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CRYSTALLIZATION

Cryst allizat ion is one of t he oldest unit operat ions in t he port f olio of indust rial and/ or laborat or y separat ions. Almost all separat ion
t echniques involve f ormat ion of a second phase f rom a f eed, and processing condit ions must be select ed t hat allow relat ively easy
segregat ion of t he t wo or more result ing phases. This is a requirement f or cryst allizat ion also, and t here are a variet y of ot her propert ies of
t he solid product t hat must be considered in t he design and operat ion of a cryst allizer. I nt eract ions among process, f unct ion, product , and
phenomena import ant in cryst allizat ion are illust rat ed in Figure 1.
Fig. 1. Cryst allizat ion.
Function. Figure 1 list s several possible f unct ions t hat can be achieved by cryst allizat ion: separat ion, purif icat ion, concent rat ion,
solidif icat ion, and analysis. A f ew examples f ollow.
Separation. Sodium carbonat e (soda ash) is recovered f rom a brine by f irst cont act ing t he brine wit h carbon dioxide t o f orm
sodium bicarbonat e. Sodium bicarbonat e has a lower solubilit y t han sodium carbonat e, and it can be r eadily cryst allized. The primary
f unct ion of cryst allizat ion in t his process is separat ion; a high percent age of sodium bicarbonat e i s solidif ied in a f orm t hat makes
subsequent separat ion of t he cryst als f rom t he mot her liquor economical. Wit h t he available pressure drop across f ilt ers t hat separat e liquid
and solid, t he capacit y of t he process is det ermined by t he rat e at which liquor f lows t hrough t he f ilt er cake. That rat e is set by t he cryst al
size dist ribut ion produced in t he cryst allizer.
Separat ion of a chemical species f rom a mixt ure of similar compounds can also be achieved by melt cr yst allizat ion, which is, f or
example, an import ant means of separat ing para-xylene (p-xylene) f rom t he ort ho and met a isomers. p-X ylene is cryst allized at t he t op of a
vert ical column and cryst als are moved downward count ercurrent ly t o liquid. The liquid f lowing upwar d is generat ed by adding heat t o melt
t he cryst als at t he bot t om of t he column; a port ion of t he melt is removed as product and t he remainder f lows up t he column t o cont act t he
downward-f lowing cryst als. Ef f luent mot her liquor, consist ing almost ent irely of t he ort ho and met a isomers of xylene, is removed f rom t he
t op of t he column.
Concentration. The concent rat ion of f ruit juice requires removal of solvent (wat er) f rom t he nat ural juice. This is commonly
done by evaporat ion, but t he derived juices may lose f lavor component s or undergo t hermal degradat ion during evaporat ion. I n f reeze
concent rat ion, solvent is cryst allized (f rozen) in a relat ively pure f orm t o leave behind a solut ion wit h a solut e concent rat ion higher t han t he
original mixt ure. Signif icant advant ages in product t ast e have been observed in t he applicat ion of t his process t o concent rat ion of cert ain
f ruit juices.
Purification. The object ive of cryst allizat ion also can be purif icat ion of a chemical species. For example, L -isoleucine (an
essent ial amino acid) is separat ed by cryst allizat ion f rom a f erment at ion brot h t hat has been f ilt ered and subject ed t o ion exchange. The
recovered cryst als cont ain impurit ies delet erious t o use of t he product , and t hese cryst als are, t heref ore, redissolved and recryst allized t o
enhance purit y.
Solidification. Product ion of a product in a f orm suit able f or use and accept able t o t he consumer also may be an obj ect ive of a
cryst allizat ion process. For example, t he appearance of sucrose (sugar) varies wit h local cust oms, and deviat ions f rom t hat cust om could
CRYSTALLIZATION
Cryst allizat ion is one of t he oldest unit operat ions in t he port f olio of indust rial and/ or laborat or y separat ions. Almost all separat ion
t echniques involve f ormat ion of a second phase f rom a f eed, and processing condit ions must be select ed t hat allow relat ively easy
segregat ion of t he t wo or more result ing phases. This is a requirement f or cryst allizat ion also, and t here are a variet y of ot her propert ies of
t he solid product t hat must be considered in t he design and operat ion of a cryst allizer. I nt eract ions among process, f unct ion, product , and
phenomena import ant in cryst allizat ion are illust rat ed in Figure 1.
Fig. 1. Cryst allizat ion.
Function. Figure 1 list s several possible f unct ions t hat can be achieved by cryst allizat ion: separat ion, purif icat ion, concent rat ion,
solidif icat ion, and analysis. A f ew examples f ollow.
Separation. Sodium carbonat e (soda ash) is recovered f rom a brine by f irst cont act ing t he brine wit h carbon dioxide t o f orm
sodium bicarbonat e. Sodium bicarbonat e has a lower solubilit y t han sodium carbonat e, and it can be r eadily cryst allized. The primary
f unct ion of cryst allizat ion in t his process is separat ion; a high percent age of sodium bicarbonat e i s solidif ied in a f orm t hat makes
subsequent separat ion of t he cryst als f rom t he mot her liquor economical. Wit h t he available pressure drop across f ilt ers t hat separat e liquid
and solid, t he capacit y of t he process is det ermined by t he rat e at which liquor f lows t hrough t he f ilt er cake. That rat e is set by t he cryst al
size dist ribut ion produced in t he cryst allizer.
Separat ion of a chemical species f rom a mixt ure of similar compounds can also be achieved by melt cr yst allizat ion, which is, f or
example, an import ant means of separat ing para-xylene (p-xylene) f rom t he ort ho and met a isomers. p-X ylene is cryst allized at t he t op of a
vert ical column and cryst als are moved downward count ercurrent ly t o liquid. The liquid f lowing upwar d is generat ed by adding heat t o melt
t he cryst als at t he bot t om of t he column; a port ion of t he melt is removed as product and t he remainder f lows up t he column t o cont act t he
downward-f lowing cryst als. Ef f luent mot her liquor, consist ing almost ent irely of t he ort ho and met a isomers of xylene, is removed f rom t he
t op of t he column.
Concentration. The concent rat ion of f ruit juice requires removal of solvent (wat er) f rom t he nat ural juice. This is commonly
done by evaporat ion, but t he derived juices may lose f lavor component s or undergo t hermal degradat ion during evaporat ion. I n f reeze
concent rat ion, solvent is cryst allized (f rozen) in a relat ively pure f orm t o leave behind a solut ion wit h a solut e concent rat ion higher t han t he
original mixt ure. Signif icant advant ages in product t ast e have been observed in t he applicat ion of t his process t o concent rat ion of cert ain
f ruit juices.
Purification. The object ive of cryst allizat ion also can be purif icat ion of a chemical species. For example, L -isoleucine (an
essent ial amino acid) is separat ed by cryst allizat ion f rom a f erment at ion brot h t hat has been f ilt ered and subject ed t o ion exchange. The
recovered cryst als cont ain impurit ies delet erious t o use of t he product , and t hese cryst als are, t heref ore, redissolved and recryst allized t o
enhance purit y.
Solidification. Product ion of a product in a f orm suit able f or use and accept able t o t he consumer also may be an obj ect ive of a
cryst allizat ion process. For example, t he appearance of sucrose (sugar) varies wit h local cust oms, and deviat ions f rom t hat cust om could
CRYSTALLIZATION Vol 7
Kirk-Othmer Encyclopedia of Chemical Technology (4th Edition) 1
lead t o an unaccept able product . A f inal cryst allizat ion may t hus be called f or t o bring t he product appearance int o compliance wit h
expect at ions.
Analysis. Many analyt ical procedures calling f or det erminat ion of molecular st ruct ure are aided by cryst allizat ion or require t hat
t he unknown compound be cryst alline. Met hodologies coupling cryst allizat ion and analyt ical procedures will not be covered here (see
X -RAY TECH N OL OGY)
Products. I n all of t he inst ances in which cryst allizat ion is used t o carry out a specif ic f unct ion, product r equirement s are a
cent ral component in det ermining t he ult imat e success of t he process. These requirement s grow out of how t he product is t o be used and
t he processing st eps bet ween cryst allizat ion and recovery of t he f inal product . K ey det erminant s of product qualit y are t he size dist ribut ion
(including mean and spread), t he morphology (including habit or shape and f orm), and purit y. Of t hese, only t he last is import ant wit h
ot her separat ion processes.
Cryst al size dist ribut ion (CSD ) det ermines several import ant processing and product propert ies, including cryst al appearance,
separat ion of cryst als f rom liquor, react ions, dissolut ion and ot her processes and propert ies involving surf ace area of t he cryst alline product ,
cryst al t ransport at ion, and cryst al st orage. I n f act , experience indicat es t hat a large f ract ion of cryst allizer t roubleshoot ing cases have been
init iat ed t o solve problems associat ed wit h inadequat e t hroughput of f ilt ers or cent rif uges; when solut ions are f ound t hey generally involve
manipulat ion of CSD .
I t is of t en import ant t o cont rol t he CSD of pharmaceut ical compounds, eg, in t he synt hesis of human insulin, which is made by
recombinant D N A t echniques (1). The most f avored size dist ribut ion is one t hat is monodisperse, ie, all cryst als are of t he same size, so
t hat t he rat e at which t he cryst als dissolve and are t aken up by t he body is known and reproducible. Such unif ormit y can be achieved by
screening or ot herwise separat ing t he desired size f rom a broader dist ribut ion or by devising a cryst allizat ion process t hat will produce
insulin in t he desired f orm. The lat t er of t hese opt ions is pref erable, and considerable ef f ort has been expended in t hat regard.
Process. I n each of t he syst ems discussed above t here is a need t o f orm cryst als, t o cause t he cryst als t o gr ow, and t o separat e t he
cryst als f rom residual liquid. There are various ways t o accomplish t hese object ives leading t o a mult it ude of processes t hat are designed t o
meet requirement s of product yield, purit y, and, uniquely, cryst al size dist ribut ion.
Phenomena. The crit ical phenomena in cryst allizat ion are, as shown in Figure 1, nucleat ion and growt h kinet ics, int erf acial
phenomena, breakage, and agglomerat ion. N ucleat ion leads t o t he f ormat ion of cryst als, eit her f rom a solut ion or a melt . Growt h is t he
enlargement of cryst als caused by deposit ion of solid mat erial on an exist ing surf ace. The relat ive rat es at which nucleat ion and growt h
occur det ermine t he cryst al size dist ribut ion; qualit at ively, when t he rat e of nucleat ion is high relat ive t o growt h rat e, cryst als f ormed are
small and numerous. Agglomerat ion is t he f ormat ion of a larger part icle t hrough t wo or more smaller part icles (cryst als) st icking t oget her. I t
is prevalent in many processes, and agglomerat ion can be essent ial f or solidliquid separat ion or it can be undesirable because it may
adversely af f ect cryst al qualit y. Breakage of cryst als is almost always undesirable because it is det riment al t o cryst al appearance and it can
lead t o excessive f ines and have a delet erious ef f ect on cryst al purit y. I nt erf acial phenomena inf luence solidliquid separat ion, f low
charact erist ics of slurries, agglomerat ion, and cryst al morphology.
SolidLiquid E quilibria and M ass and E nergy Balances
Solubility. Solidliquid equilibrium, or t he solubilit y of a chemical compound in a solvent , ref ers t o t he amount of solut e t hat can
be dissolved at const ant t emperat ure, pressure, and syst em composit ion; in ot her words, t he maximum concent rat ion of t he solut e in t he
solvent at st at ic condit ions. I n a syst em consist ing of a solut e and a solvent , specif ying syst em t emperat ure and pressure f ixes all ot her
int ensive variables. I n part icular, t he composit ion of each of t he t wo phases is f ixed, and solubili t y diagrams of t he t ype shown f or a
hypot het ical mixt ure of R and S in Figure 2 can be const ruct ed. Such a syst em is said t o f orm an eut ect ic, ie, t here is a condit ion at which
bot h R and S cryst allize int o a solid phase at a f ixed rat io t hat is ident ical t o t heir rat io in sol ut ion. Consequent ly, t here is no change in t he
composit ion of residual liquor as a result of cryst allizat ion.
lead t o an unaccept able product . A f inal cryst allizat ion may t hus be called f or t o bring t he product appearance int o compliance wit h
expect at ions.
Analysis. Many analyt ical procedures calling f or det erminat ion of molecular st ruct ure are aided by cryst allizat ion or require t hat
t he unknown compound be cryst alline. Met hodologies coupling cryst allizat ion and analyt ical procedures will not be covered here (see
X -RAY TECH N OL OGY)
Products. I n all of t he inst ances in which cryst allizat ion is used t o carry out a specif ic f unct ion, product r equirement s are a
cent ral component in det ermining t he ult imat e success of t he process. These requirement s grow out of how t he product is t o be used and
t he processing st eps bet ween cryst allizat ion and recovery of t he f inal product . K ey det erminant s of product qualit y are t he size dist ribut ion
(including mean and spread), t he morphology (including habit or shape and f orm), and purit y. Of t hese, only t he last is import ant wit h
ot her separat ion processes.
Cryst al size dist ribut ion (CSD ) det ermines several import ant processing and product propert ies, including cryst al appearance,
separat ion of cryst als f rom liquor, react ions, dissolut ion and ot her processes and propert ies involving surf ace area of t he cryst alline product ,
cryst al t ransport at ion, and cryst al st orage. I n f act , experience indicat es t hat a large f ract ion of cryst allizer t roubleshoot ing cases have been
init iat ed t o solve problems associat ed wit h inadequat e t hroughput of f ilt ers or cent rif uges; when solut ions are f ound t hey generally involve
manipulat ion of CSD .
I t is of t en import ant t o cont rol t he CSD of pharmaceut ical compounds, eg, in t he synt hesis of human insulin, which is made by
recombinant D N A t echniques (1). The most f avored size dist ribut ion is one t hat is monodisperse, ie, all cryst als are of t he same size, so
t hat t he rat e at which t he cryst als dissolve and are t aken up by t he body is known and reproducible. Such unif ormit y can be achieved by
screening or ot herwise separat ing t he desired size f rom a broader dist ribut ion or by devising a cryst allizat ion process t hat will produce
insulin in t he desired f orm. The lat t er of t hese opt ions is pref erable, and considerable ef f ort has been expended in t hat regard.
Process. I n each of t he syst ems discussed above t here is a need t o f orm cryst als, t o cause t he cryst als t o gr ow, and t o separat e t he
cryst als f rom residual liquid. There are various ways t o accomplish t hese object ives leading t o a mult it ude of processes t hat are designed t o
meet requirement s of product yield, purit y, and, uniquely, cryst al size dist ribut ion.
Phenomena. The crit ical phenomena in cryst allizat ion are, as shown in Figure 1, nucleat ion and growt h kinet ics, int erf acial
phenomena, breakage, and agglomerat ion. N ucleat ion leads t o t he f ormat ion of cryst als, eit her f rom a solut ion or a melt . Growt h is t he
enlargement of cryst als caused by deposit ion of solid mat erial on an exist ing surf ace. The relat ive rat es at which nucleat ion and growt h
occur det ermine t he cryst al size dist ribut ion; qualit at ively, when t he rat e of nucleat ion is high relat ive t o growt h rat e, cryst als f ormed are
small and numerous. Agglomerat ion is t he f ormat ion of a larger part icle t hrough t wo or more smaller part icles (cryst als) st icking t oget her. I t
is prevalent in many processes, and agglomerat ion can be essent ial f or solidliquid separat ion or it can be undesirable because it may
adversely af f ect cryst al qualit y. Breakage of cryst als is almost always undesirable because it is det riment al t o cryst al appearance and it can
lead t o excessive f ines and have a delet erious ef f ect on cryst al purit y. I nt erf acial phenomena inf luence solidliquid separat ion, f low
charact erist ics of slurries, agglomerat ion, and cryst al morphology.
SolidLiquid E quilibria and M ass and E nergy Balances
Solubility. Solidliquid equilibrium, or t he solubilit y of a chemical compound in a solvent , ref ers t o t he amount of solut e t hat can
be dissolved at const ant t emperat ure, pressure, and syst em composit ion; in ot her words, t he maximum concent rat ion of t he solut e in t he
solvent at st at ic condit ions. I n a syst em consist ing of a solut e and a solvent , specif ying syst em t emperat ure and pressure f ixes all ot her
int ensive variables. I n part icular, t he composit ion of each of t he t wo phases is f ixed, and solubili t y diagrams of t he t ype shown f or a
hypot het ical mixt ure of R and S in Figure 2 can be const ruct ed. Such a syst em is said t o f orm an eut ect ic, ie, t here is a condit ion at which
bot h R and S cryst allize int o a solid phase at a f ixed rat io t hat is ident ical t o t heir rat io in sol ut ion. Consequent ly, t here is no change in t he
composit ion of residual liquor as a result of cryst allizat ion.
CRYSTALLIZATION Vol 7
Kirk-Othmer Encyclopedia of Chemical Technology (4th Edition) 2
Fig. 2. Solubilit y diagram f or a hypot het ical syst em. The curves AB and BC represent solut ion composit ions t hat are in equilibrium wit h
solids whose composit ions are given by t he lines AD and CE. I f AD and CE are vert ical along t he respect ive axes, t he cryst als are pure R
and S, respect ively. Cryst allizat ion f rom any solut ion whose composit ion is t o t he lef t of t he vert ical li ne t hrough point B produces cryst als
of pure R, whereas solut ions t o t he right of t he line produce cryst als of pure S. A solut ion whose composit ion f alls on t he line t hrough B
produces a solid mixt ure t hat has a composit ion ident ical t o t he liquid solut ion.
Several f eat ures of t he hypot het ical syst em in Figure 2 can be used t o illust rat e proper select ion of cryst allizer operat ing condit ions
and limit at ions placed on t he operat ion by syst em propert ies. Suppose a sat urat ed solut ion at t emper at ure T
1
is f ed t o a cryst allizer
operat ing at t emperat ure T
2
. Because t he f eed is sat urat ed, t he weight f ract ion of S in t he f eed is given as shown in Figure 2. The maximum
cryst al product ion rat e P
max
f rom such a process depends on t he value of T
2
and is given by
P
max
= F x
F
L x
L
(1)
where F is t he f eed rat e t o t he cryst allizer, and L is t he solut ion f low rat e leaving t he cryst allizer. N o ot her st ream is f ed t o or removed f rom
t he cryst allizer. N ot e t hat t he lower limit on T
2
is given by t he eut ect ic point B.
Figure 3 present s t he equilibrium behavior of magnesium sulf at e in wat er, and it is illust rat ive of syst ems t hat f orm hydrat ed salt s.
Equilibrium solut ion concent rat ions are plot t ed as curves ab, bc, cd, de, and ef; t he solid phases t hat are in equilibrium wit h t hese solut ions
have composit ions given by t he lines ag, hi , j k , l m, and no, respect ively. I ce is t he solid phase whose composit ion is given by ag, and cryst als
cont aining dif f ering rat ios of wat er of hydrat ion t o magnesium sulf at e const it ut e t he solids represent ed by t he ot her lines. Specif ically, t he
line no represent s magnesium sulf at e monohydrat e (MgSO
4
H
2
O), which has one wat er molecule per molecule of magnesium sulf at e,
whereas t he lines ml , k j , and i h represent t he hexahydrat e, hept ahydrat e, and dodecahydrat e f orms, respect ively. The weight f ract ion of
MgSO
4
in each of t he cryst al f orms is shown in Figure 3, and as wit h all cryst alline mat erials having wat er of hydrat ion, t he solut e balance of
equat ion 1 must be modif ied t o read
x
c
P
max
= F x
F
L x
L
(2)
where x
c
is t he mass f ract ion of solut e in t he cryst al, eg, x
c
is 0.488 when t he cryst alline subst ance is magnesium sulf at e hept ahydrat e.
D if f erences in t he f orms of magnesium sulf at e cryst als af f ect t he dependence of solubilit y on t emper at ure, which is ref lect ed by t he slopes
of t he solut ion composit ion curves.
Fig. 2. Solubilit y diagram f or a hypot het ical syst em. The curves AB and BC represent solut ion composit ions t hat are in equilibrium wit h
solids whose composit ions are given by t he lines AD and CE. I f AD and CE are vert ical along t he respect ive axes, t he cryst als are pure R
and S, respect ively. Cryst allizat ion f rom any solut ion whose composit ion is t o t he lef t of t he vert ical li ne t hrough point B produces cryst als
of pure R, whereas solut ions t o t he right of t he line produce cryst als of pure S. A solut ion whose composit ion f alls on t he line t hrough B
produces a solid mixt ure t hat has a composit ion ident ical t o t he liquid solut ion.
Several f eat ures of t he hypot het ical syst em in Figure 2 can be used t o illust rat e proper select ion of cryst allizer operat ing condit ions
and limit at ions placed on t he operat ion by syst em propert ies. Suppose a sat urat ed solut ion at t emper at ure T
1
is f ed t o a cryst allizer
operat ing at t emperat ure T
2
. Because t he f eed is sat urat ed, t he weight f ract ion of S in t he f eed is given as shown in Figure 2. The maximum
cryst al product ion rat e P
max
f rom such a process depends on t he value of T
2
and is given by
P
max
= F x
F
L x
L
(1)
where F is t he f eed rat e t o t he cryst allizer, and L is t he solut ion f low rat e leaving t he cryst allizer. N o ot her st ream is f ed t o or removed f rom
t he cryst allizer. N ot e t hat t he lower limit on T
2
is given by t he eut ect ic point B.
Figure 3 present s t he equilibrium behavior of magnesium sulf at e in wat er, and it is illust rat ive of syst ems t hat f orm hydrat ed salt s.
Equilibrium solut ion concent rat ions are plot t ed as curves ab, bc, cd, de, and ef; t he solid phases t hat are in equilibrium wit h t hese solut ions
have composit ions given by t he lines ag, hi , j k , l m, and no, respect ively. I ce is t he solid phase whose composit ion is given by ag, and cryst als
cont aining dif f ering rat ios of wat er of hydrat ion t o magnesium sulf at e const it ut e t he solids represent ed by t he ot her lines. Specif ically, t he
line no represent s magnesium sulf at e monohydrat e (MgSO
4
H
2
O), which has one wat er molecule per molecule of magnesium sulf at e,
whereas t he lines ml , k j , and i h represent t he hexahydrat e, hept ahydrat e, and dodecahydrat e f orms, respect ively. The weight f ract ion of
MgSO
4
in each of t he cryst al f orms is shown in Figure 3, and as wit h all cryst alline mat erials having wat er of hydrat ion, t he solut e balance of
equat ion 1 must be modif ied t o read
x
c
P
max
= F x
F
L x
L
(2)
where x
c
is t he mass f ract ion of solut e in t he cryst al, eg, x
c
is 0.488 when t he cryst alline subst ance is magnesium sulf at e hept ahydrat e.
D if f erences in t he f orms of magnesium sulf at e cryst als af f ect t he dependence of solubilit y on t emper at ure, which is ref lect ed by t he slopes
of t he solut ion composit ion curves.
CRYSTALLIZATION Vol 7
Kirk-Othmer Encyclopedia of Chemical Technology (4th Edition) 3
Fig. 3. Solubilit y diagram f or magnesium sulf at e in wat er.
The dependence of solubilit y on t emperat ure af f ect s t he mode of cryst allizat ion. For example, Figure 4 shows t hat t he solubilit y of
pot assium nit rat e is st rongly inf luenced by t he syst em t emperat ure but t hat t emperat ure has lit t le inf luence on t he solubilit y of sodium
chloride. As a consequence, a reasonable yield of K N O
3
cryst als can be obt ained by cooling a sat urat ed f eed solut ion; on t he ot her hand,
cooling a sat urat ed sodium chloride solut ion accomplishes lit t le cryst allizat ion, and evaporat ion is required t o increase t he yield of sodium
chloride cryst als.
Fig. 4. Solubilit ies of N aCl " , and K N O
3
, in wat er.
The product ion of many high value chemicals requires maximizing separat ion f rom a relat ively dilut e solut ion. I t is common in such
Fig. 3. Solubilit y diagram f or magnesium sulf at e in wat er.
The dependence of solubilit y on t emperat ure af f ect s t he mode of cryst allizat ion. For example, Figure 4 shows t hat t he solubilit y of
pot assium nit rat e is st rongly inf luenced by t he syst em t emperat ure but t hat t emperat ure has lit t le inf luence on t he solubilit y of sodium
chloride. As a consequence, a reasonable yield of K N O
3
cryst als can be obt ained by cooling a sat urat ed f eed solut ion; on t he ot her hand,
cooling a sat urat ed sodium chloride solut ion accomplishes lit t le cryst allizat ion, and evaporat ion is required t o increase t he yield of sodium
chloride cryst als.
Fig. 4. Solubilit ies of N aCl " , and K N O
3
, in wat er.
The product ion of many high value chemicals requires maximizing separat ion f rom a relat ively dilut e solut ion. I t is common in such
CRYSTALLIZATION Vol 7
Kirk-Othmer Encyclopedia of Chemical Technology (4th Edition) 4
inst ances t o use a combinat ion of met hods t o reduce solut e solubilit y in t he f eed solut ion. Figure 5, f or example, illust rat es t hat t he addit ion
of met hanol t o a sat urat ed aqueous solut ion of L -serine can reduce solubilit y by more t han an order of magnit ude.
Fig. 5. Solubilit ies of L -serine in mixt ures of met hanol and wat er. Relat ive solubility = solubility in CH
3
OH H
2
O solubility in H
2
O; ,
10C: " , 30C. Reproduced by permission of t he American I nst it ut e of Chemical Engineers (4).
Solubilit y dat a can be f ound in a variet y of unit s, and conversion f rom one set of unit s t o anot her of t en is required bef ore
comput at ion of yield can be perf ormed. Guides t o such conversions are available. I t is of t en most convenient , however, t o express
solubilit y and composit ions in mixed st reams in t erms of mass rat ios, ie, mass of solut e per mass of solvent .
Supersaturation. The t hermodynamic driving f orce f or bot h cryst al nucleat ion and growt h is t he key variable in set t ing t he
mechanisms and rat es by which t hese processes occur. Supersat urat ion is def ined rigorously as t he deviat ion f rom t hermodynamic
equilibrium, which is t he dif f erence bet ween t he chemical pot ent ial of t he solut e at t he exist ing condit ions of t he syst em u and t he chemical
pot ent ial of t he solut e equilibrat ed at t he syst em condit ions u* . L ess abst ract def init ions involving measurable syst em propert ies such as
t emperat ure, concent rat ion, or mass or mole f ract ion also have been used t o express supersat urat ion. Consider, f or example, a syst em at
t emperat ure T wit h a solut e concent rat ion c. A sat urat ed solut ion having a concent rat ion c would be at t emperat ure T * , whereas a sat urat ed
solut ion having a t emperat ure T would have a solut e concent rat ion c* .
Expressions of supersat urat ion can t hen be f ormulat ed as f ollows: (1) t he dif f erence bet ween t he chemical pot ent ial of t he syst em
and t he chemical pot ent ial of at sat urat ion,

, where t he chemical pot ent ial is a f unct ion of bot h t emperat ure and concent rat ion; (2)
t he dif f erence bet ween t he solut e concent rat ion and t he concent rat ion at equilibrium, c c

; (3) t he dif f erence bet ween t he syst em


t emperat ure at equilibrium and t he act ual t emperat ure, T

T; (4) t he rat io of t he solut e concent rat ion and t he equilibrium concent rat ion,
c/ c* , which is known as relat ive sat urat ion; or (5) t he rat io of t he dif f erence bet ween t he solut e concent rat ion and t he equilibrium
concent rat ion t o t he equilibrium concent rat ion, s = (c c

)=c

, which is known as relat ive supersat urat ion. This t erm has of t en been
represent ed by o; s is used here because of t he f requent use of o f or int erf acial energy or surf ace t ension and f or variance in dist ribut ion
f unct ions.
Any of t hese def init ions of supersat urat ion can be used over a moderat e range of syst em condit ions. For example, a dif f erence in
chemical pot ent ial =

is proport ional t o bot h c c

and T

T over a modest range of condit ions. Of t he f ive expressions


given, however, t he second is most usef ul in calculat ing t he yield f rom a cryst allizer, t he t hird pr ovides inf ormat ion t hat may be most usef ul
in t he cont rol of a cryst allizer, and t he f if t h is most commonly used in correlat ing t he dependence of nucleat ion and growt h kinet ics on
supersat urat ion.
Alt hough t he f irst of t hese expressions is t he most nearly f undament ally correct , it is dif f icult t o evaluat e because of inadequat e
capabilit ies of det ermining chemical pot ent ial as a f unct ion of t emperat ure and composit ion. The next most appropriat e driving f orce f or
cryst al growt h is t hat given by t he last of t he possibilit ies, ie, s = (c c

)=c

. This def init ion of supersat urat ion will be used t hroughout t he
ensuing discussion, but it should be recognized t hat t he validit y of doing so is limit ed t o low supersat urat ions. Solut e concent rat ions used in
det ermining supersat urat ion should include any wat er of hydrat ion associat ed wit h t he solut e in t he cryst al at equilibrium.
M ass and E nergy Balances. The f ormulat ion of mass and energy balances f ollows procedures out lined in many basic t ext s
(2). The use of solubilit ies t o calculat e cryst al product ion rat es f rom a cooling cryst allizer was demonst rat ed by t he discussion of equat ions 1
and 2. Subsequent t o det ermining t he yield, t he rat e at which heat must be removed f rom such a cryst allizer can be calculat ed f rom an
energy balance:
F
b
H
F
= P
b
H
C
+ L
b
H
L
+ Q
inst ances t o use a combinat ion of met hods t o reduce solut e solubilit y in t he f eed solut ion. Figure 5, f or example, illust rat es t hat t he addit ion
of met hanol t o a sat urat ed aqueous solut ion of L -serine can reduce solubilit y by more t han an order of magnit ude.
Fig. 5. Solubilit ies of L -serine in mixt ures of met hanol and wat er. Relat ive solubility = solubility in CH
3
OH H
2
O solubility in H
2
O; ,
10C: " , 30C. Reproduced by permission of t he American I nst it ut e of Chemical Engineers (4).
Solubilit y dat a can be f ound in a variet y of unit s, and conversion f rom one set of unit s t o anot her of t en is required bef ore
comput at ion of yield can be perf ormed. Guides t o such conversions are available. I t is of t en most convenient , however, t o express
solubilit y and composit ions in mixed st reams in t erms of mass rat ios, ie, mass of solut e per mass of solvent .
Supersaturation. The t hermodynamic driving f orce f or bot h cryst al nucleat ion and growt h is t he key variable in set t ing t he
mechanisms and rat es by which t hese processes occur. Supersat urat ion is def ined rigorously as t he deviat ion f rom t hermodynamic
equilibrium, which is t he dif f erence bet ween t he chemical pot ent ial of t he solut e at t he exist ing condit ions of t he syst em u and t he chemical
pot ent ial of t he solut e equilibrat ed at t he syst em condit ions u* . L ess abst ract def init ions involving measurable syst em propert ies such as
t emperat ure, concent rat ion, or mass or mole f ract ion also have been used t o express supersat urat ion. Consider, f or example, a syst em at
t emperat ure T wit h a solut e concent rat ion c. A sat urat ed solut ion having a concent rat ion c would be at t emperat ure T * , whereas a sat urat ed
solut ion having a t emperat ure T would have a solut e concent rat ion c* .
Expressions of supersat urat ion can t hen be f ormulat ed as f ollows: (1) t he dif f erence bet ween t he chemical pot ent ial of t he syst em
and t he chemical pot ent ial of at sat urat ion,

, where t he chemical pot ent ial is a f unct ion of bot h t emperat ure and concent rat ion; (2)
t he dif f erence bet ween t he solut e concent rat ion and t he concent rat ion at equilibrium, c c

; (3) t he dif f erence bet ween t he syst em


t emperat ure at equilibrium and t he act ual t emperat ure, T

T; (4) t he rat io of t he solut e concent rat ion and t he equilibrium concent rat ion,
c/ c* , which is known as relat ive sat urat ion; or (5) t he rat io of t he dif f erence bet ween t he solut e concent rat ion and t he equilibrium
concent rat ion t o t he equilibrium concent rat ion, s = (c c

)=c

, which is known as relat ive supersat urat ion. This t erm has of t en been
represent ed by o; s is used here because of t he f requent use of o f or int erf acial energy or surf ace t ension and f or variance in dist ribut ion
f unct ions.
Any of t hese def init ions of supersat urat ion can be used over a moderat e range of syst em condit ions. For example, a dif f erence in
chemical pot ent ial =

is proport ional t o bot h c c

and T

T over a modest range of condit ions. Of t he f ive expressions


given, however, t he second is most usef ul in calculat ing t he yield f rom a cryst allizer, t he t hird pr ovides inf ormat ion t hat may be most usef ul
in t he cont rol of a cryst allizer, and t he f if t h is most commonly used in correlat ing t he dependence of nucleat ion and growt h kinet ics on
supersat urat ion.
Alt hough t he f irst of t hese expressions is t he most nearly f undament ally correct , it is dif f icult t o evaluat e because of inadequat e
capabilit ies of det ermining chemical pot ent ial as a f unct ion of t emperat ure and composit ion. The next most appropriat e driving f orce f or
cryst al growt h is t hat given by t he last of t he possibilit ies, ie, s = (c c

)=c

. This def init ion of supersat urat ion will be used t hroughout t he
ensuing discussion, but it should be recognized t hat t he validit y of doing so is limit ed t o low supersat urat ions. Solut e concent rat ions used in
det ermining supersat urat ion should include any wat er of hydrat ion associat ed wit h t he solut e in t he cryst al at equilibrium.
M ass and E nergy Balances. The f ormulat ion of mass and energy balances f ollows procedures out lined in many basic t ext s
(2). The use of solubilit ies t o calculat e cryst al product ion rat es f rom a cooling cryst allizer was demonst rat ed by t he discussion of equat ions 1
and 2. Subsequent t o det ermining t he yield, t he rat e at which heat must be removed f rom such a cryst allizer can be calculat ed f rom an
energy balance:
F
b
H
F
= P
b
H
C
+ L
b
H
L
+ Q
CRYSTALLIZATION Vol 7
Kirk-Othmer Encyclopedia of Chemical Technology (4th Edition) 5
(3)
where F , P, and L are f eed rat e, cryst al product ion rat e, and mot her liquor f low rat e, respect ively; > is t he specif ic ent halpy of t he st ream
corresponding t o t he subscript ; and Q is t he required rat e of heat t ransf er. As F , P, and L are known or can be calculat ed f rom a simple
mass balance, det erminat ion of Q requires met hods of est imat ing specif ic ent halpies.
I f appropriat e ent halpy dat a are unavailable, est imat es can be obt ained by f irst def ining ref erence st at es f or bot h solut e and solvent .
Of t en t he most convenient ref erence st at es are cryst alline solut e and pure solvent at an arbit rarily chosen ref erence t emperat ure. The
ref erence t emperat ure select ed usually corresponds t o t hat at which t he heat of cryst allizat ion A>
C
of t he solut e is known. The heat of
cryst allizat ion is approximat ely equal t o t he negat ive of t he heat of solut ion. For example, if t he heat of cryst al lizat ion is known at T
ref
, t hen
reasonable ref erence condit ions would be t he solut e as a solid and t he solvent as a liquid, bot h at T
ref
. The specif ic ent halpies t hen could be
evaluat ed as
b
H
F
= x
F

b
H
C
+ C
pF
(T T
r ef
)
(4)
b
H
C
= C
pC
(T T
r ef
)
(5)
b
H
L
= x
L

b
H
C
+ C
pL
(T T
r ef
)
(6)
where x
F
and x
L
are t he mass f ract ions of solut e in t he f eed and mot her liquor, respect ively. All t hat is required now t o det ermine t he
required rat e of heat t ransf er is t he indicat ed heat capacit ies, which can be est imat ed or measured experiment ally.
N ow suppose some of t he solvent is evaporat ed in t he cryst allizer, as is shown in Figure 6. I ndependent balances can be writ t en on
t ot al mass and solut e:
F = V + L + P
(7)
x
F
F = x
L
L + x
C
P
(8)
where F = feed rat e, V = vapor wit hdrawal rat e, L = liquid (f ilt rat e) wit hdrawal rat e, and P = cryst al product ion rat e, and x
j
= solut e
cont ent of st ream j in unit s consist ent wit h f low rat e. There is an equilibrium expression relat ing x
L
, x
C
, and t he t emperat ure or pressure at
which t he operat ion is conduct ed. I n addit ion, an energy balance must be sat isf ied:
F
b
H
F
+ Q = V
b
H
V
+ L
b
H
L
+ P
b
H
C
(9)
The specif ic ent halpies (>
j
) in equat ion 9 can be det ermined as described earlier, provided t he t emperat ures of t he product st reams are
known. Evaporat ive cooling cryst allizers operat e at reduced pressure and may be considered adiabat ic (Q = 0). As wit h of many problems
involving equilibrium relat ionships and mass and energy balances, t rial-and-error comput at ions are of t en involved in solving equat ions 7
t hrough 9.
(3)
where F , P, and L are f eed rat e, cryst al product ion rat e, and mot her liquor f low rat e, respect ively; > is t he specif ic ent halpy of t he st ream
corresponding t o t he subscript ; and Q is t he required rat e of heat t ransf er. As F , P, and L are known or can be calculat ed f rom a simple
mass balance, det erminat ion of Q requires met hods of est imat ing specif ic ent halpies.
I f appropriat e ent halpy dat a are unavailable, est imat es can be obt ained by f irst def ining ref erence st at es f or bot h solut e and solvent .
Of t en t he most convenient ref erence st at es are cryst alline solut e and pure solvent at an arbit rarily chosen ref erence t emperat ure. The
ref erence t emperat ure select ed usually corresponds t o t hat at which t he heat of cryst allizat ion A>
C
of t he solut e is known. The heat of
cryst allizat ion is approximat ely equal t o t he negat ive of t he heat of solut ion. For example, if t he heat of cryst al lizat ion is known at T
ref
, t hen
reasonable ref erence condit ions would be t he solut e as a solid and t he solvent as a liquid, bot h at T
ref
. The specif ic ent halpies t hen could be
evaluat ed as
b
H
F
= x
F

b
H
C
+ C
pF
(T T
r ef
)
(4)
b
H
C
= C
pC
(T T
r ef
)
(5)
b
H
L
= x
L

b
H
C
+ C
pL
(T T
r ef
)
(6)
where x
F
and x
L
are t he mass f ract ions of solut e in t he f eed and mot her liquor, respect ively. All t hat is required now t o det ermine t he
required rat e of heat t ransf er is t he indicat ed heat capacit ies, which can be est imat ed or measured experiment ally.
N ow suppose some of t he solvent is evaporat ed in t he cryst allizer, as is shown in Figure 6. I ndependent balances can be writ t en on
t ot al mass and solut e:
F = V + L + P
(7)
x
F
F = x
L
L + x
C
P
(8)
where F = feed rat e, V = vapor wit hdrawal rat e, L = liquid (f ilt rat e) wit hdrawal rat e, and P = cryst al product ion rat e, and x
j
= solut e
cont ent of st ream j in unit s consist ent wit h f low rat e. There is an equilibrium expression relat ing x
L
, x
C
, and t he t emperat ure or pressure at
which t he operat ion is conduct ed. I n addit ion, an energy balance must be sat isf ied:
F
b
H
F
+ Q = V
b
H
V
+ L
b
H
L
+ P
b
H
C
(9)
The specif ic ent halpies (>
j
) in equat ion 9 can be det ermined as described earlier, provided t he t emperat ures of t he product st reams are
known. Evaporat ive cooling cryst allizers operat e at reduced pressure and may be considered adiabat ic (Q = 0). As wit h of many problems
involving equilibrium relat ionships and mass and energy balances, t rial-and-error comput at ions are of t en involved in solving equat ions 7
t hrough 9.
CRYSTALLIZATION Vol 7
Kirk-Othmer Encyclopedia of Chemical Technology (4th Edition) 6
Fig. 6. Schemat ic diagram of a simple cryst allizer.
The mass balance on a cryst allizer is relat ed t o t he growt h kinet ics t hat occur wit hin t he unit . Thi s may be illust rat ed by considering
syst ems in which cryst al growt h kinet ics are suf f icient ly f ast t o use essent ially all of t he supersat urat ion provided by t he cryst allizer. Under
such condit ions (ref erred t o in t he cryst allizat ion lit erat ure as class I I or f ast -growt h behavior), t he solut e concent rat ion in t he mot her liquor
can be assigned a value corresponding t o sat urat ion. Alt ernat ively, should supersat urat ion in t he mot her liquor be so great as t o af f ect t he
solut e balance, t he operat ion is said t o f ollow class I or slow-growt h behavior. An expression coupl ing t he rat e of growt h t o a solut e balance
must be used t o describe such a syst em.
Crystallization Kinetics
Along wit h operat ing variables of t he cryst allizer, nucleat ion and growt h det ermine such cryst al charact erist ics as size dist ribut ion, purit y,
and shape or habit .
N ucleation. Cryst al nucleat ion is t he f ormat ion of an ordered solid phase f rom a liquid or amorphous phase. N ucleat ion set s t he
charact er of t he cryst allizat ion process, and it is, t heref ore, t he most crit ical component in relat ing cryst allizer design and operat ion t o
cryst al size dist ribut ions.
M echanisms. Classical nucleat ion t heory is based on homogeneous and het erogeneous mechanisms, bot h of which call f or t he
f ormat ion of cryst als t hrough a process of sequent ially combining t he const it uent unit s t hat f orm a cryst al. Het erogeneous and
homogeneous mechanisms are ref erred t o as primary nucleat ion because exist ing cryst als play no role in t he nucleat ion. Primary nucleat ion
can be illust rat ed by considering a hypot het ical experiment in t he cont ext of t he solubilit y dat a in Figure 7. Assume t hat a solut ion is at a
concent rat ion and t emperat ure corresponding t o point A on t he f igure. The solut ion is undersat urat ed, so any cryst als present in t he syst em
would dissolve. I f t he concent rat ion is increased at const ant t emperat ure, f or example by evaporat ion, t he pat h f ollowed would cause t he
solut ion t o reach sat urat ed condit ions at point B. Once t he concent rat ion becomes great er t han t hat at B, t he solut ion is supersat urat ed and
any cryst als present in t he syst em would grow. However, experience shows t hat nucleat ion would not occur unt il t he concent rat ion reaches
point C, which def ines what is called t he met ast able limit . I f t his procedure is repeat ed at various t emperat ures, a met ast able limit curve
could be drawn as shown.
Fig. 7. Solubilit y and primary nucleat ion in a hypot het ical experiment .
Wit hin t he met ast able region, primary nucleat ion will not occur, and t he widt h of t he met ast able zone, as ref lect ed by c
m
c

or
T

T
m
, varies f rom one subst ance t o anot her. Furt hermore, t he widt h can vary f or t he same subst ance wit h composit ion, t he presence of
impurit ies t hat alt er int erf acial t ension, and various ot her f act ors.
Bot h homogeneous and het erogeneous mechanisms require relat ively high supersat urat ion, and t hey exhi bit a high order dependence
on supersat urat ion. These f act ors of t en lead t o product ion of excessive f ines in syst ems where primary nucleat ion mechanisms are
import ant . The classical t heoret ical t reat ment of primary nucleat ion result s in t he expression (5):
B
0
= A exp

16
3

2
3k
3
T
3
[ln(s + 1) ]
2
!
Fig. 6. Schemat ic diagram of a simple cryst allizer.
The mass balance on a cryst allizer is relat ed t o t he growt h kinet ics t hat occur wit hin t he unit . Thi s may be illust rat ed by considering
syst ems in which cryst al growt h kinet ics are suf f icient ly f ast t o use essent ially all of t he supersat urat ion provided by t he cryst allizer. Under
such condit ions (ref erred t o in t he cryst allizat ion lit erat ure as class I I or f ast -growt h behavior), t he solut e concent rat ion in t he mot her liquor
can be assigned a value corresponding t o sat urat ion. Alt ernat ively, should supersat urat ion in t he mot her liquor be so great as t o af f ect t he
solut e balance, t he operat ion is said t o f ollow class I or slow-growt h behavior. An expression coupl ing t he rat e of growt h t o a solut e balance
must be used t o describe such a syst em.
Crystallization Kinetics
Along wit h operat ing variables of t he cryst allizer, nucleat ion and growt h det ermine such cryst al charact erist ics as size dist ribut ion, purit y,
and shape or habit .
N ucleation. Cryst al nucleat ion is t he f ormat ion of an ordered solid phase f rom a liquid or amorphous phase. N ucleat ion set s t he
charact er of t he cryst allizat ion process, and it is, t heref ore, t he most crit ical component in relat ing cryst allizer design and operat ion t o
cryst al size dist ribut ions.
M echanisms. Classical nucleat ion t heory is based on homogeneous and het erogeneous mechanisms, bot h of which call f or t he
f ormat ion of cryst als t hrough a process of sequent ially combining t he const it uent unit s t hat f orm a cryst al. Het erogeneous and
homogeneous mechanisms are ref erred t o as primary nucleat ion because exist ing cryst als play no role in t he nucleat ion. Primary nucleat ion
can be illust rat ed by considering a hypot het ical experiment in t he cont ext of t he solubilit y dat a in Figure 7. Assume t hat a solut ion is at a
concent rat ion and t emperat ure corresponding t o point A on t he f igure. The solut ion is undersat urat ed, so any cryst als present in t he syst em
would dissolve. I f t he concent rat ion is increased at const ant t emperat ure, f or example by evaporat ion, t he pat h f ollowed would cause t he
solut ion t o reach sat urat ed condit ions at point B. Once t he concent rat ion becomes great er t han t hat at B, t he solut ion is supersat urat ed and
any cryst als present in t he syst em would grow. However, experience shows t hat nucleat ion would not occur unt il t he concent rat ion reaches
point C, which def ines what is called t he met ast able limit . I f t his procedure is repeat ed at various t emperat ures, a met ast able limit curve
could be drawn as shown.
Fig. 7. Solubilit y and primary nucleat ion in a hypot het ical experiment .
Wit hin t he met ast able region, primary nucleat ion will not occur, and t he widt h of t he met ast able zone, as ref lect ed by c
m
c

or
T

T
m
, varies f rom one subst ance t o anot her. Furt hermore, t he widt h can vary f or t he same subst ance wit h composit ion, t he presence of
impurit ies t hat alt er int erf acial t ension, and various ot her f act ors.
Bot h homogeneous and het erogeneous mechanisms require relat ively high supersat urat ion, and t hey exhi bit a high order dependence
on supersat urat ion. These f act ors of t en lead t o product ion of excessive f ines in syst ems where primary nucleat ion mechanisms are
import ant . The classical t heoret ical t reat ment of primary nucleat ion result s in t he expression (5):
B
0
= A exp

16
3

2
3k
3
T
3
[ln(s + 1) ]
2
!
CRYSTALLIZATION Vol 7
Kirk-Othmer Encyclopedia of Chemical Technology (4th Edition) 7
(10)
where k is t he Bolt zmann const ant , o is surf ace energy per unit area, v is molar volume, and A is a const ant . This equat ion can be
simplif ied by recognizing t hat ln (s + 1) approaches s as s approaches 0. So f or small supersat urat ions,
B
0
= A exp

16
3

2
3k
3
T
3
s
2

(11)
The most import ant variables af f ect ing nucleat ion rat e are shown by equat ions 10 and 11 t o be int erf acial energy, t emperat ure, and
supersat urat ion.
The high order dependence of nucleat ion rat e on supersat urat ion is especially import ant because a small swing in supersat urat ion
may produce an enormous change in nucleat ion rat e. This gives rise t o t he of t en-observed phenomenon of having a clear liquor
t ransf ormed t o a slurry of f ine cryst als wit h only a slight increase in supersat urat ion, f or example, by decreasing t he solut ion
t emperat ure.
The cat alyt ic ef f ect of solid part icles (as in het erogeneous nucleat ion) is t o reduce t he energy bar rier t o f ormat ion of a new phase.
This, in ef f ect , can reduce t he int erf acial energy o signif icant ly.
The met ast able limit can provide an empirical approach t o modeling primary nucleat ion. This limit , which was f irst observed in 1951
(6), must be det ermined t hrough experiment at ion, and nucleat ion rat e is correlat ed wit h t he f ollowing equat ion
B
0
= k(c c
m
)
i
(12)
where t he equilibrium concent rat ion c* is less t han t he concent rat ion at t he met ast able limit , c
m
. Values of c
m
are of t en very close t o c* f or
many inorganic syst ems, and sat isf act ory correlat ions have been obt ained wit h c* subst it ut ed f or c
m
in equat ion 12 (7); in ot her words,
B
0
= k(c c

)
i
(13)
where t he paramet ers k and i must be evaluat ed f rom experiment al dat a.
Secondary nucleat ion is cryst al f ormat ion t hrough a mechanism involving t he solut e cryst als; cryst als of t he solut e must be present
f or secondary nucleat ion t o occur. Thorough reviews have been given (8,9).
Several f eat ures of secondary nucleat ion make it more import ant t han primary nucleat ion in indust rial cryst allizers. First , cont inuous
cryst allizers and seeded bat ch cryst allizers have cryst als in t he magma t hat can part icipat e in secondary nucleat ion mechanisms. Second, t he
requirement s f or t he mechanisms of secondary nucleat ion t o be operat ive are f ulf illed easily in most indust rial cryst allizers. Finally, low
supersat urat ion can support secondary nucleat ion but not primary nucleat ion, and most cryst allizers are operat ed in a low supersat urat ion
regime t hat improves yield and enhances product purit y and cryst al morphology.
Secondary nucleat ion can occur as t he result of several mechanisms t hat have been ident if ied in select ed syst ems and include t he
f ollowing. I ni ti al breedi ng result s f rom immersion of seed cryst als in a supersat urat ed solut ion. I t is t hought t o be caused by dislodging
ext remely small cryst als t hat were f ormed on t he surf ace of larger cryst als during drying. Alt hough t his mechanism is unimport ant in
cont inuous and unseeded bat ch cryst allizat ion, it can be signif icant in t he operat ion of seeded bat ch cryst allizers. Several process variables
have been shown t o inf luence nucleat ion rat es caused by init ial breeding (10). Contact nucl eati on result s f rom collisions of cryst als wit h one
anot her, and/ or cryst allizer int ernals, and/ or an impeller in an agit at or or circulat ion pump. The collision energy required f or cont act
nucleat ion is small and does not result in macroscopic degradat ion (breakage) of t he cont act ed cryst al. Shear breedi ng result s when
supersat urat ed solut ion f lows by a cryst al surf ace and carries wit h it cryst al precursors believed f ormed in t he region of t he growing cryst al
surf ace. I n a st udy of nucleat ion of MgSO
4
7H
2
O by t his mechanism, it was f ound (11) t hat high levels of supersat urat ion were required f or
it t o produce signif icant numbers of nuclei.
Process Variables Affecting Contact N ucleation. Pioneering st udies elucidat ed many f act ors af f ect ing cont act nucleat ion
(1214). The number of cryst als produced by a cont rolled impact of an object wit h a seed cryst al depends on energy of impact ,
supersat urat ion at impact , supersat urat ion at which cryst als mat ure, hardness of t he impact ing object , area of impact , angle of impact , and
syst em t emperat ure. Alt hough it is impossible t o account quant it at ively f or all of t hese variables, cert ain generalizat ions can be drawn f rom
t he research on t his nucleat ion mechanism.
Based on experiment al observat ions, t he f ollowing expression was proposed (15) f or syst ems at const ant supersat urat ion:
B
0
= k
N
exp(E E
t
)
(14)
The same researchers proposed t hat a relat ionship of impact energy E t o cryst allizer variables must include t he mass of t he impact ing
(10)
where k is t he Bolt zmann const ant , o is surf ace energy per unit area, v is molar volume, and A is a const ant . This equat ion can be
simplif ied by recognizing t hat ln (s + 1) approaches s as s approaches 0. So f or small supersat urat ions,
B
0
= A exp

16
3

2
3k
3
T
3
s
2

(11)
The most import ant variables af f ect ing nucleat ion rat e are shown by equat ions 10 and 11 t o be int erf acial energy, t emperat ure, and
supersat urat ion.
The high order dependence of nucleat ion rat e on supersat urat ion is especially import ant because a small swing in supersat urat ion
may produce an enormous change in nucleat ion rat e. This gives rise t o t he of t en-observed phenomenon of having a clear liquor
t ransf ormed t o a slurry of f ine cryst als wit h only a slight increase in supersat urat ion, f or example, by decreasing t he solut ion
t emperat ure.
The cat alyt ic ef f ect of solid part icles (as in het erogeneous nucleat ion) is t o reduce t he energy bar rier t o f ormat ion of a new phase.
This, in ef f ect , can reduce t he int erf acial energy o signif icant ly.
The met ast able limit can provide an empirical approach t o modeling primary nucleat ion. This limit , which was f irst observed in 1951
(6), must be det ermined t hrough experiment at ion, and nucleat ion rat e is correlat ed wit h t he f ollowing equat ion
B
0
= k(c c
m
)
i
(12)
where t he equilibrium concent rat ion c* is less t han t he concent rat ion at t he met ast able limit , c
m
. Values of c
m
are of t en very close t o c* f or
many inorganic syst ems, and sat isf act ory correlat ions have been obt ained wit h c* subst it ut ed f or c
m
in equat ion 12 (7); in ot her words,
B
0
= k(c c

)
i
(13)
where t he paramet ers k and i must be evaluat ed f rom experiment al dat a.
Secondary nucleat ion is cryst al f ormat ion t hrough a mechanism involving t he solut e cryst als; cryst als of t he solut e must be present
f or secondary nucleat ion t o occur. Thorough reviews have been given (8,9).
Several f eat ures of secondary nucleat ion make it more import ant t han primary nucleat ion in indust rial cryst allizers. First , cont inuous
cryst allizers and seeded bat ch cryst allizers have cryst als in t he magma t hat can part icipat e in secondary nucleat ion mechanisms. Second, t he
requirement s f or t he mechanisms of secondary nucleat ion t o be operat ive are f ulf illed easily in most indust rial cryst allizers. Finally, low
supersat urat ion can support secondary nucleat ion but not primary nucleat ion, and most cryst allizers are operat ed in a low supersat urat ion
regime t hat improves yield and enhances product purit y and cryst al morphology.
Secondary nucleat ion can occur as t he result of several mechanisms t hat have been ident if ied in select ed syst ems and include t he
f ollowing. I ni ti al breedi ng result s f rom immersion of seed cryst als in a supersat urat ed solut ion. I t is t hought t o be caused by dislodging
ext remely small cryst als t hat were f ormed on t he surf ace of larger cryst als during drying. Alt hough t his mechanism is unimport ant in
cont inuous and unseeded bat ch cryst allizat ion, it can be signif icant in t he operat ion of seeded bat ch cryst allizers. Several process variables
have been shown t o inf luence nucleat ion rat es caused by init ial breeding (10). Contact nucl eati on result s f rom collisions of cryst als wit h one
anot her, and/ or cryst allizer int ernals, and/ or an impeller in an agit at or or circulat ion pump. The collision energy required f or cont act
nucleat ion is small and does not result in macroscopic degradat ion (breakage) of t he cont act ed cryst al. Shear breedi ng result s when
supersat urat ed solut ion f lows by a cryst al surf ace and carries wit h it cryst al precursors believed f ormed in t he region of t he growing cryst al
surf ace. I n a st udy of nucleat ion of MgSO
4
7H
2
O by t his mechanism, it was f ound (11) t hat high levels of supersat urat ion were required f or
it t o produce signif icant numbers of nuclei.
Process Variables Affecting Contact N ucleation. Pioneering st udies elucidat ed many f act ors af f ect ing cont act nucleat ion
(1214). The number of cryst als produced by a cont rolled impact of an object wit h a seed cryst al depends on energy of impact ,
supersat urat ion at impact , supersat urat ion at which cryst als mat ure, hardness of t he impact ing object , area of impact , angle of impact , and
syst em t emperat ure. Alt hough it is impossible t o account quant it at ively f or all of t hese variables, cert ain generalizat ions can be drawn f rom
t he research on t his nucleat ion mechanism.
Based on experiment al observat ions, t he f ollowing expression was proposed (15) f or syst ems at const ant supersat urat ion:
B
0
= k
N
exp(E E
t
)
(14)
The same researchers proposed t hat a relat ionship of impact energy E t o cryst allizer variables must include t he mass of t he impact ing
CRYSTALLIZATION Vol 7
Kirk-Othmer Encyclopedia of Chemical Technology (4th Edition) 8
cryst al m
c
, t he rot at ional velocit y of t he impeller providing mixing e, and t he f ract ion of t he available energy act ually t ransmit t ed t o t he
cryst al c:
E = f (! ; ; m
c
)
(15)
Correlat ions of nucleat ion rat es wit h cryst allizer variables have been developed f or a variet y of syst ems. Alt hough t he correlat ions are
empirical, a mechanist ic hypot hesis regarding nucleat ion can be helpf ul in select ing operat ing variables f or inclusion in t he model. Two
examples are (1) t he ef f ect of slurry circulat ion rat e on nucleat ion has been used t o develop a correlat ion f or nucleat ion rat e based on t he
t ip speed of t he impeller (16) and (2) t he scaleup of nucleat ion kinet ics f or sodium chloride cryst allizat ion provided an analysis of t he role of
mixing and mixer charact erist ics in cont act nucleat ion (17). Published kinet ic correlat ions have been reviewed t hrough about 1979 (18). I n a
lat er sect ion on populat ion balances, simple power-law expressions are used t o correlat e nucleat ion rat e dat a and describe t he ef f ect of
nucleat ion on cryst al size dist ribut ion.
Supersat urat ion has been observed t o af f ect cont act nucleat ion, but t he mechanism by which t his occurs is not clear. There are dat a
(19) t hat inf er a direct relat ionship bet ween cont act nucleat ion and cryst al growt h. This relat ionship has been explained by showing t hat t he
ef f ect of supersat urat ion on cont act nucleat ion must consider t he reduct ion in int erf acial supersat urat ion due t o t he resist ance t o dif f usion
or convect ive mass t ransf er (20).
St ill anot her possible role of supersat urat ion is t hat it af f ect s t he solut ion st ruct ure and causes t he f ormat ion of clust ers of solut e
molecules. These clust ers may part icipat e in nucleat ion, alt hough t he mechanism by which t his would occur is not clear. Evidence of t he
exist ence of clust er f ormat ion in supersat urat ed solut ions has been present ed f or cit ric acid (21); while ot hers have examined t he
phenomenon in great er det ail (22,23).
The ease wit h which nuclei can be produced by cont act nucleat ion is a clear indicat ion t hat t his mechanism is dominant in many
indust rial operat ions. Research on cont act nucleat ion is cont inuing wit h t he object ive of building an underst anding of t he phenomenon t hat
will allow it s successf ul inclusion in models describing commercial syst ems.
Crystal Growth. At least t wo resist ances det ermine growt h kinet ics, t hose associat ed wit h int egrat ion or incorporat i on of t he
cryst alline unit (f or example, solut e molecules) int o t he cryst al surf ace (lat t ice) and molecular or bulk t ransport of t he unit f rom t he
surrounding solut ion t o t he cryst al f ace. The primary concern here is wit h surf ace incorporat ion. A simple set of experiment s in which t he
rat e of advance of a cryst al f ace is measured can be used t o illust rat e t hese t wo resist ances. D at a given in Figure 8 show t he ef f ect of
solut ion velocit y over a cryst al f ace at t hree dif f erent condit ions. As t he solut ion velocit y increases f rom low values, t he growt h rat es also
increase. At about 24 cm/ s, however, t he growt h rat es approach const ant values. Such behavior indicat es t hat bot h bulk mass t ransf er and
surf ace incorporat ion are import ant below 24 cm/ s but above t his velocit y, surf ace incorporat ion provides t he dominant resist ance t o
growt h.
Fig. 8. Ef f ect of solut ion velocit y on t he growt h rat e of t he < 110 > f ace of MgSO
4
7H
2
O. Concent rat ion of MgSO
4
: , 29.02% wt % at
30.8C; , 28.89 wt % at 30.8C; " , 18.89 wt % at 31.3C.
Growth M odels. N umerous models have been proposed t o describe surf ace react ion kinet ics, including t hose t hat assume
cryst als grow by layers and ot hers t hat consider growt h t o occur by t he movement of a cont inuous st ep. Each model result s in a specif ic
relat ionship bet ween growt h rat e and supersat urat ion, but none can be used f or a priori predict ions of growt h kinet ics. I nsight s regarding
t he roles of cert ain process variables can be obt ained, however, and wit h addit ional research predict ive capabilit ies may be achieved. For
t hese reasons and because of t he ext ensive lit erat ure on t he subject (5,2426) all t hat will be point ed out here are t he key aspect s of t he
physical models and t he result ing relat ionship bet ween growt h and supersat urat ion predict ed by each t heory.
cryst al m
c
, t he rot at ional velocit y of t he impeller providing mixing e, and t he f ract ion of t he available energy act ually t ransmit t ed t o t he
cryst al c:
E = f (! ; ; m
c
)
(15)
Correlat ions of nucleat ion rat es wit h cryst allizer variables have been developed f or a variet y of syst ems. Alt hough t he correlat ions are
empirical, a mechanist ic hypot hesis regarding nucleat ion can be helpf ul in select ing operat ing variables f or inclusion in t he model. Two
examples are (1) t he ef f ect of slurry circulat ion rat e on nucleat ion has been used t o develop a correlat ion f or nucleat ion rat e based on t he
t ip speed of t he impeller (16) and (2) t he scaleup of nucleat ion kinet ics f or sodium chloride cryst allizat ion provided an analysis of t he role of
mixing and mixer charact erist ics in cont act nucleat ion (17). Published kinet ic correlat ions have been reviewed t hrough about 1979 (18). I n a
lat er sect ion on populat ion balances, simple power-law expressions are used t o correlat e nucleat ion rat e dat a and describe t he ef f ect of
nucleat ion on cryst al size dist ribut ion.
Supersat urat ion has been observed t o af f ect cont act nucleat ion, but t he mechanism by which t his occurs is not clear. There are dat a
(19) t hat inf er a direct relat ionship bet ween cont act nucleat ion and cryst al growt h. This relat ionship has been explained by showing t hat t he
ef f ect of supersat urat ion on cont act nucleat ion must consider t he reduct ion in int erf acial supersat urat ion due t o t he resist ance t o dif f usion
or convect ive mass t ransf er (20).
St ill anot her possible role of supersat urat ion is t hat it af f ect s t he solut ion st ruct ure and causes t he f ormat ion of clust ers of solut e
molecules. These clust ers may part icipat e in nucleat ion, alt hough t he mechanism by which t his would occur is not clear. Evidence of t he
exist ence of clust er f ormat ion in supersat urat ed solut ions has been present ed f or cit ric acid (21); while ot hers have examined t he
phenomenon in great er det ail (22,23).
The ease wit h which nuclei can be produced by cont act nucleat ion is a clear indicat ion t hat t his mechanism is dominant in many
indust rial operat ions. Research on cont act nucleat ion is cont inuing wit h t he object ive of building an underst anding of t he phenomenon t hat
will allow it s successf ul inclusion in models describing commercial syst ems.
Crystal Growth. At least t wo resist ances det ermine growt h kinet ics, t hose associat ed wit h int egrat ion or incorporat i on of t he
cryst alline unit (f or example, solut e molecules) int o t he cryst al surf ace (lat t ice) and molecular or bulk t ransport of t he unit f rom t he
surrounding solut ion t o t he cryst al f ace. The primary concern here is wit h surf ace incorporat ion. A simple set of experiment s in which t he
rat e of advance of a cryst al f ace is measured can be used t o illust rat e t hese t wo resist ances. D at a given in Figure 8 show t he ef f ect of
solut ion velocit y over a cryst al f ace at t hree dif f erent condit ions. As t he solut ion velocit y increases f rom low values, t he growt h rat es also
increase. At about 24 cm/ s, however, t he growt h rat es approach const ant values. Such behavior indicat es t hat bot h bulk mass t ransf er and
surf ace incorporat ion are import ant below 24 cm/ s but above t his velocit y, surf ace incorporat ion provides t he dominant resist ance t o
growt h.
Fig. 8. Ef f ect of solut ion velocit y on t he growt h rat e of t he < 110 > f ace of MgSO
4
7H
2
O. Concent rat ion of MgSO
4
: , 29.02% wt % at
30.8C; , 28.89 wt % at 30.8C; " , 18.89 wt % at 31.3C.
Growth M odels. N umerous models have been proposed t o describe surf ace react ion kinet ics, including t hose t hat assume
cryst als grow by layers and ot hers t hat consider growt h t o occur by t he movement of a cont inuous st ep. Each model result s in a specif ic
relat ionship bet ween growt h rat e and supersat urat ion, but none can be used f or a priori predict ions of growt h kinet ics. I nsight s regarding
t he roles of cert ain process variables can be obt ained, however, and wit h addit ional research predict ive capabilit ies may be achieved. For
t hese reasons and because of t he ext ensive lit erat ure on t he subject (5,2426) all t hat will be point ed out here are t he key aspect s of t he
physical models and t he result ing relat ionship bet ween growt h and supersat urat ion predict ed by each t heory.
CRYSTALLIZATION Vol 7
Kirk-Othmer Encyclopedia of Chemical Technology (4th Edition) 9
Models used t o describe t he growt h of cryst als by layers call f or a t wo-st ep process: (1) f ormat ion of a t wo-dimensional nucleus on
t he surf ace and (2) spreading of t he solut e f rom t he t wo-dimensional nucleus across t he surf ace. The relat ive rat es at which t hese t wo st eps
occur give rise t o t he mononuclear t wo-dimensional nucleat ion t heory and t he polynuclear t wo-dimensi onal nucleat ion t heory. I n t he
mononuclear t wo-dimensional nucleat ion t heory, t he surf ace nucleat ion st ep occurs at a f init e rat e, whereas t he spreading across t he surf ace
is assumed t o occur at an inf init e rat e. The reverse is t rue f or t he polynuclear t wo-dimensional nucleat ion t heory. From t he mononuclear
t wo-dimensional nucleat ion t heory, growt h is relat ed t o supersat urat ion by t he equat ion.
G = C
1
hA[ln(1+ s) ]
1=2
exp

C
2
T
2
ln(1+ s)

(16)
where C
1
and C
2
are syst em-dependent const ant s, h is t he height of t he nucleus, A is surf ace area, and s and T are as def ined earlier. The
polynuclear t wo-dimensional t heory produces t he equat ion
G =

C
3
T
2
[ln(1+ s) ]
3=2
!
exp

C
2
T
2
ln(1+ s)

(17)
where C
3
is a syst em-dependent const ant . Finally, if bot h f ormat ion of t he t wo-dimensional nucleus and spreading of t he surf ace layer are
import ant in det ermining growt h rat e, t he f ollowing equat ion can be derived:
G = C
4
s
2=3
[ln(1 + s) ]
1=6
exp

C
2
3T
2
ln(1+ s)

(18)
where C
4
is a syst em-dependent const ant .
Equat ion 1618 can be simplif ied considerably by recognizing t hat in many syst ems t he quant it y s is much less t han 1. I n t hat case,
ln(1+ s) is approximat ely s. Making t his subst it ut ion, t he growt h rat e f rom t he mononuclear t wo-dimensional nucleat ion t heory becomes
G = C
1
hAs
1=2
exp

C
2
T
2
s

(19)
For t he polynuclear t wo-dimensional nucleat ion t heory
G =

C
3
T
2
s
3=2

exp

C
2
T
2
s

(20)
For bot h st eps occurring at similar rat es
G = C
4
s
5=6
exp

C
2
T
2
s

(21)
The screw dislocat ion t heory (27), of t en ref erred t o as t he BCF t heory (af t er it s f ormulat ors), shows t hat t he dependence of growt h
rat e on supersat urat ion can vary f rom a parabolic relat ionship at low supersat urat ion t o a linear relat ionship at high supersat urat ion. I n t he
BCF t heory, growt h rat e is given by
G = C

s
2

0
1

t anh

0
1
s

(22)
where is screw dislocat ion act ivit y and o'
1
is a syst em-dependent quant it y t hat is inversely proport ional t o t emperat ure. The dependence
of growt h rat e on supersat urat ion is linear if t he rat io
0
1
=s is large, but t he dependence becomes parabolic as t he rat io becomes small. This
is because (

0
1
s
) !

0
1
s
as

0
1
s
becomes small (supersat urat ion becomes large), and (

0
1
s
) ! 1:0 as

0
1
s
becomes large (supersat urat ion becomes
small). I t is t hus possible t o observe variat ions in t he dependence of growt h rat e on supersat urat ion f or a given cryst al-solvent syst em.
An empirical approach can also be used t o relat e growt h kinet ics t o supersat urat ion wit h a power-law f unct ion of t he f orm
G = k
G
s
g
Models used t o describe t he growt h of cryst als by layers call f or a t wo-st ep process: (1) f ormat ion of a t wo-dimensional nucleus on
t he surf ace and (2) spreading of t he solut e f rom t he t wo-dimensional nucleus across t he surf ace. The relat ive rat es at which t hese t wo st eps
occur give rise t o t he mononuclear t wo-dimensional nucleat ion t heory and t he polynuclear t wo-dimensi onal nucleat ion t heory. I n t he
mononuclear t wo-dimensional nucleat ion t heory, t he surf ace nucleat ion st ep occurs at a f init e rat e, whereas t he spreading across t he surf ace
is assumed t o occur at an inf init e rat e. The reverse is t rue f or t he polynuclear t wo-dimensional nucleat ion t heory. From t he mononuclear
t wo-dimensional nucleat ion t heory, growt h is relat ed t o supersat urat ion by t he equat ion.
G = C
1
hA[ln(1+ s) ]
1=2
exp

C
2
T
2
ln(1+ s)

(16)
where C
1
and C
2
are syst em-dependent const ant s, h is t he height of t he nucleus, A is surf ace area, and s and T are as def ined earlier. The
polynuclear t wo-dimensional t heory produces t he equat ion
G =

C
3
T
2
[ln(1+ s) ]
3=2
!
exp

C
2
T
2
ln(1+ s)

(17)
where C
3
is a syst em-dependent const ant . Finally, if bot h f ormat ion of t he t wo-dimensional nucleus and spreading of t he surf ace layer are
import ant in det ermining growt h rat e, t he f ollowing equat ion can be derived:
G = C
4
s
2=3
[ln(1 + s) ]
1=6
exp

C
2
3T
2
ln(1+ s)

(18)
where C
4
is a syst em-dependent const ant .
Equat ion 1618 can be simplif ied considerably by recognizing t hat in many syst ems t he quant it y s is much less t han 1. I n t hat case,
ln(1+ s) is approximat ely s. Making t his subst it ut ion, t he growt h rat e f rom t he mononuclear t wo-dimensional nucleat ion t heory becomes
G = C
1
hAs
1=2
exp

C
2
T
2
s

(19)
For t he polynuclear t wo-dimensional nucleat ion t heory
G =

C
3
T
2
s
3=2

exp

C
2
T
2
s

(20)
For bot h st eps occurring at similar rat es
G = C
4
s
5=6
exp

C
2
T
2
s

(21)
The screw dislocat ion t heory (27), of t en ref erred t o as t he BCF t heory (af t er it s f ormulat ors), shows t hat t he dependence of growt h
rat e on supersat urat ion can vary f rom a parabolic relat ionship at low supersat urat ion t o a linear relat ionship at high supersat urat ion. I n t he
BCF t heory, growt h rat e is given by
G = C

s
2

0
1

t anh

0
1
s

(22)
where is screw dislocat ion act ivit y and o'
1
is a syst em-dependent quant it y t hat is inversely proport ional t o t emperat ure. The dependence
of growt h rat e on supersat urat ion is linear if t he rat io
0
1
=s is large, but t he dependence becomes parabolic as t he rat io becomes small. This
is because (

0
1
s
) !

0
1
s
as

0
1
s
becomes small (supersat urat ion becomes large), and (

0
1
s
) ! 1:0 as

0
1
s
becomes large (supersat urat ion becomes
small). I t is t hus possible t o observe variat ions in t he dependence of growt h rat e on supersat urat ion f or a given cryst al-solvent syst em.
An empirical approach can also be used t o relat e growt h kinet ics t o supersat urat ion wit h a power-law f unct ion of t he f orm
G = k
G
s
g
CRYSTALLIZATION Vol 7
Kirk-Othmer Encyclopedia of Chemical Technology (4th Edition) 10
(23)
where k
G
and g are const ant s det ermined by f it t ing t he equat ion t o growt h-rat e dat a. Such an approach should be valid over small ranges of
supersat urat ion, and analysis of t he t heories discussed above shows t hat t he more f undament al equat i ons can be f it by equat ion 23 over
limit ed ranges of supersat urat ion. For example, using t he empirical approach t o describe syst ems in which t he screw dislocat ion model was
applicable would limit g t o values bet ween 1 and 2, assuming c was independent of supersat urat ion.
All t he models described above indicat e t he import ance of syst em t emperat ure on growt h rat e. D ependencies of growt h kinet ics on
t emperat ure are of t en expressed in t erms of an Arrhenius expression:
k
G
= k
0
G
exp

E
G
RT

(24)
where k
G
is a growt h rat e coef f icient of t he t ype required in equat ion 23, k
0
G
is a const ant , and AE
G
is an act ivat ion energy. The magnit ude
of AE
G
can be as large as t hat f or many chemical react ions, 42 kJ/ mol (>10 kcal =mol ).
Bot h supersat urat ion and t emperat ure can have dif f erent ef f ect s on t he growt h rat es of dif f erent f aces of t he same cryst al. Such
occurrences have implicat ions wit h respect t o cryst al habit , and t hese are dealt wit h in a lat er sect ion.
E ffects of I mpurities and Solvent. The presence of impurit ies usually decreases t he growt h rat es of cryst alline mat erials, and
problems associat ed wit h t he product ion of cryst als smaller t han desired are commonly at t ribut ed t o cont aminat ion of f eed solut ions. St rict
prot ocols should be f ollowed in operat ing unit s upst ream f rom a cryst allizer t o minimize t he possibi lit y of such occurrences. Equally
import ant is monit oring t he composit ion of recycle st reams so as t o det ect possible accumulat ion of impurit ies. Furt hermore, cryst allizat ion
kinet ics used in scaleup should be obt ained f rom experiment s on solut ions as similar as possible t o t hose expect ed in t he f ull-scale
process.
The ef f ect s of a solvent on growt h rat es have been at t ribut ed t o t wo set s of f act ors (28): one has t o do wit h t he ef f ect s of solvent on
mass t ransf er of t he solut e t hrough adjust ment s in viscosit y, densit y, and dif f usivit y; t he second i s concerned wit h t he st ruct ure of t he
int erf ace bet ween cryst al and solvent . The analysis (28) concludes t hat a solut e-solvent syst em t hat has a high solubilit y is likely t o produce a
rough int erf ace and, concomit ant ly, large cryst al growt h rat es.
Crystal Growth in M ixed Crystallizers. Mult icryst al magma st udies usually involve examinat ion of t he rat e of change of a
charact erist ic cryst al dimension or t he rat e of increase in t he mass of cryst als. The charact erist ic dimension depends on t he met hod used in
t he det erminat ion of size; eg, t he second-largest dimension is measured by sieve analyses, whereas bot h elect ronic-zone-sensing and
laser-light -scat t ering inst rument s provide est imat es of an equivalent spherical diamet er. I f t he rat e of change of a cryst al mass dM
c
/ dt is
measured, t he quant it y can be relat ed t o t he rat e of change in t he cryst al charact erist ic dimension by t he equat ion
dM
c
dt
=
d

c
k
v
L
3

dt
= 3
c
k
v
L
2
dL
dt
(25)
where p
c
is cryst al densit y and k
v
is t he volume shape f act or. Because an area shape f act or can be def ined by t he equat ion
k
a
= A
c
=L
2
(26)
and G is def ined as dL / dt,
dM
c
dt
= 3
c

k
v
k
a

A
c
G
(27)
The f ormulat ion of a populat ion balance requires def ining growt h rat e as t he rat e of change of t he charact erist ic dimension
G =
dL
dt
(28)
and solut ion of t he result ing dif f erent ial populat ion balance requires a knowledge of t he relat ionship bet ween growt h rat e and size of t he
growing cryst als. Moreover, t his relat ionship can of t en be deduced f rom t he f orm of populat ion densi t y dat a. A special condit ion, which
simplif ies such balances, result s when all cryst als in t he magma grow at t he same rat e. Cryst al-solvent syst ems t hat show t his behavior are
said t o f ollow t he AL law (29) whereas syst ems t hat do not are said t o exhibit anomalous growt h.
Anomalous growt h means t hat growt h rat es of cryst als in a magma are not ident ical or t hat t he growt h rat e of an individual cryst al or
mass of cryst als is not const ant . Two t heories have been used t o explain growt h rat e anomalies: size-dependent growt h and growt h rat e
(23)
where k
G
and g are const ant s det ermined by f it t ing t he equat ion t o growt h-rat e dat a. Such an approach should be valid over small ranges of
supersat urat ion, and analysis of t he t heories discussed above shows t hat t he more f undament al equat i ons can be f it by equat ion 23 over
limit ed ranges of supersat urat ion. For example, using t he empirical approach t o describe syst ems in which t he screw dislocat ion model was
applicable would limit g t o values bet ween 1 and 2, assuming c was independent of supersat urat ion.
All t he models described above indicat e t he import ance of syst em t emperat ure on growt h rat e. D ependencies of growt h kinet ics on
t emperat ure are of t en expressed in t erms of an Arrhenius expression:
k
G
= k
0
G
exp

E
G
RT

(24)
where k
G
is a growt h rat e coef f icient of t he t ype required in equat ion 23, k
0
G
is a const ant , and AE
G
is an act ivat ion energy. The magnit ude
of AE
G
can be as large as t hat f or many chemical react ions, 42 kJ/ mol (>10 kcal =mol ).
Bot h supersat urat ion and t emperat ure can have dif f erent ef f ect s on t he growt h rat es of dif f erent f aces of t he same cryst al. Such
occurrences have implicat ions wit h respect t o cryst al habit , and t hese are dealt wit h in a lat er sect ion.
E ffects of I mpurities and Solvent. The presence of impurit ies usually decreases t he growt h rat es of cryst alline mat erials, and
problems associat ed wit h t he product ion of cryst als smaller t han desired are commonly at t ribut ed t o cont aminat ion of f eed solut ions. St rict
prot ocols should be f ollowed in operat ing unit s upst ream f rom a cryst allizer t o minimize t he possibi lit y of such occurrences. Equally
import ant is monit oring t he composit ion of recycle st reams so as t o det ect possible accumulat ion of impurit ies. Furt hermore, cryst allizat ion
kinet ics used in scaleup should be obt ained f rom experiment s on solut ions as similar as possible t o t hose expect ed in t he f ull-scale
process.
The ef f ect s of a solvent on growt h rat es have been at t ribut ed t o t wo set s of f act ors (28): one has t o do wit h t he ef f ect s of solvent on
mass t ransf er of t he solut e t hrough adjust ment s in viscosit y, densit y, and dif f usivit y; t he second i s concerned wit h t he st ruct ure of t he
int erf ace bet ween cryst al and solvent . The analysis (28) concludes t hat a solut e-solvent syst em t hat has a high solubilit y is likely t o produce a
rough int erf ace and, concomit ant ly, large cryst al growt h rat es.
Crystal Growth in M ixed Crystallizers. Mult icryst al magma st udies usually involve examinat ion of t he rat e of change of a
charact erist ic cryst al dimension or t he rat e of increase in t he mass of cryst als. The charact erist ic dimension depends on t he met hod used in
t he det erminat ion of size; eg, t he second-largest dimension is measured by sieve analyses, whereas bot h elect ronic-zone-sensing and
laser-light -scat t ering inst rument s provide est imat es of an equivalent spherical diamet er. I f t he rat e of change of a cryst al mass dM
c
/ dt is
measured, t he quant it y can be relat ed t o t he rat e of change in t he cryst al charact erist ic dimension by t he equat ion
dM
c
dt
=
d

c
k
v
L
3

dt
= 3
c
k
v
L
2
dL
dt
(25)
where p
c
is cryst al densit y and k
v
is t he volume shape f act or. Because an area shape f act or can be def ined by t he equat ion
k
a
= A
c
=L
2
(26)
and G is def ined as dL / dt,
dM
c
dt
= 3
c

k
v
k
a

A
c
G
(27)
The f ormulat ion of a populat ion balance requires def ining growt h rat e as t he rat e of change of t he charact erist ic dimension
G =
dL
dt
(28)
and solut ion of t he result ing dif f erent ial populat ion balance requires a knowledge of t he relat ionship bet ween growt h rat e and size of t he
growing cryst als. Moreover, t his relat ionship can of t en be deduced f rom t he f orm of populat ion densi t y dat a. A special condit ion, which
simplif ies such balances, result s when all cryst als in t he magma grow at t he same rat e. Cryst al-solvent syst ems t hat show t his behavior are
said t o f ollow t he AL law (29) whereas syst ems t hat do not are said t o exhibit anomalous growt h.
Anomalous growt h means t hat growt h rat es of cryst als in a magma are not ident ical or t hat t he growt h rat e of an individual cryst al or
mass of cryst als is not const ant . Two t heories have been used t o explain growt h rat e anomalies: size-dependent growt h and growt h rat e
CRYSTALLIZATION Vol 7
Kirk-Othmer Encyclopedia of Chemical Technology (4th Edition) 11
dispersion. Bot h alt er t he f orm of t he populat ion densit y f unct ion obt ained f rom perf ect ly mixed cont inuous cryst allizers; unf ort unat ely,
such behavior cannot be used t o dist inguish bet ween size-dependent growt h and growt h rat e dispersion, as bot h have t he same qualit at ive
ef f ect s on populat ion densit y.
Size-dependent Crystal Growth. A number of empirical expressions correlat e t he apparent ef f ect of cryst al size on growt h
rat e (30). The most commonly used correlat ion uses t hree empirical paramet ers t o correlat e growt h rat e wit h cryst al size:
G = G
0
(1+ L)
b
; b < 1
(29)
where G
0
, , and b are det ermined f rom experiment al dat a. There have been at t empt s t o relat e t he kinet ic paramet er bt o cryst allizer
variables; t he only success in t his regard (31) showed a qualit at ive dependence on cryst allizer volume. Several t heories have been proposed
t o explain size-dependent growt h kinet ics, but none has been subst ant iat ed by direct observat ion or used t o predict t he onset of such
behavior. One explanat ion seems part icularly appealing: larger cryst als impact impellers and ot her cryst allizer int ernals wit h higher
f requency and energy t han smaller cryst als; t heref ore, t he larger cryst als are recipient s of more surf ace breaks and irregularit ies t hat lead t o
higher growt h rat es.
Growth Rate D ispersion. This phenomenon is t he exhibit ion of dif f erent growt h rat es by cryst als in a magma, even t hough
t hey may have t he same size and are exposed t o ident ical condit ions. I t is now generally accept ed t hat many observat ions originally
at t ribut ed t o size-dependent growt h were due t o growt h rat e dispersion. Such erroneous int erpret at ions were t he result of similarit ies in t he
ef f ect s of t he t wo t ypes of behavior on cryst al size dist ribut ions.
The ef f ect s of growt h rat e dispersion on a populat ion of sucrose cryst als were f irst charact erized by a linear correlat ion of t he
variance of t he populat ion about a mean size L wit h t he ext ent of growt h (30). I t was demonst rat ed lat er (32,33) t hat growt h rat e dispersion
could account f or anomalous charact erist ics in t he populat ion densit y of cryst als obt ained f rom cont inuous, st eady-st at e cryst allizers. L at er
st udies examined bat ch cryst allizat ion dat a t o show t hat apparent size-dependent growt h of pot assium alum cryst als was a manif est at ion of
growt h rat e dispersion (34). Cryst als of cit ric acid monohydrat e generat ed by cont act nucleat ion were f ound t o exhibit growt h rat e
dispersion but not size-dependent growt h (35).
Two dist inct ly dif f erent mechanisms leading t o growt h rat e dispersion have experiment al support . The f irst assumes t hat all cryst als
have t he same t ime-averaged growt h rat e, but t he growt h rat es of individual cryst als f luct uat e about some mean value (36). D irect evidence
of random f luct uat ions in growt h rat es has been report ed f or magnesium sulf at e hept ahydrat e (37) and pot assium alum (38). The second
assumes t hat cryst als are f ormed wit h a charact erist ic dist ribut ion of growt h rat es, but individual cryst als ret ain a const ant growt h rat e
t hroughout t heir residence in a cryst allizer. Findings on cit ric acid (35), pot assium nit rat e (39), and ammonium dihydrogen phosphat e (40)
support t his mechanism.
Surf ace int egrat ion is t hought t o be t he primary f act or in bot h mechanisms of growt h rat e dispersion. The BCF t heory indicat es t hat
t he growt h rat e of a cryst al f ace depends on t he number, sign, and locat ion of screw dislocat ions on t he surf ace of a growing cryst al.
Collisions of cryst als wit h each ot her and cryst allizer int ernals result in changes in t he dislocat i on net work of a cryst al, t hereby leading t o
random f luct uat ions of growt h rat es. Changes in t he dislocat ion net works also occur simply due t o t he imperf ect growt h of cryst al f aces. A
dist ribut ion of growt h rat es is a result of t he varying dislocat ion net works and densit ies among nuclei and seed cryst als.
Alt hough evidence exist s f or bot h mechanisms of growt h rat e dispersion, separat e mat hemat ical models were developed f or
incorporat ing t he t wo mechanisms int o descript ions of cryst al populat ions: random growt h rat e f luct uat ions (36) and growt h rat e
dist ribut ions (33,40). Bot h mechanisms can be included in a populat ion balance t o show t he relat ive ef f ect s of t he t wo mechanisms on
cryst al size dist ribut ions f rom bat ch and cont inuous cryst allizers (41).
Crystal Characteristics
The morphology (including cryst al shape or habit ), size dist ribut ion, and purit y of cryst alline mat erials can det ermine t he success in f ulf illing
t he f unct ion of a cryst allizat ion operat ion.
M orphology. A cryst al is highly organized, and const it uent unit s, which can be at oms, molecules, or ions, are posit ioned in a
t hree-dimensional periodic pat t ern called a space lat t ice. A charact erist ic cryst al shape result s f r om t he regular int ernal st ruct ure of t he solid
wit h cryst al surf aces f orming parallel t o planes f ormed by t he const it uent unit s. The surf aces (f aces) of a cryst al may exhibit varying degrees
of development , wit h a concomit ant variat ion in macroscopic appearance.
I f at oms, molecules, or ions of a unit cell are t reat ed as point s, t he lat t ice st ruct ure of t he ent i re cryst al can be shown t o be a
mult iplicat ion in t hree dimensions of t he unit cell. Only 14 possible lat t ices (called Bravais lat t i ces) can be drawn in t hree dimensions. These
can be classif ied int o seven groups based on t heir element s of symmet ry. Moreover, examinat ion of t he element s of symmet ry (about a
point , a line, or a plane) f or a cryst al shows t hat t here are 32 dif f erent combinat ions (classes) t hat can be grouped int o seven syst ems. The
correspondence of t hese seven syst ems t o t he seven lat t ice groups is shown in Table 1.
dispersion. Bot h alt er t he f orm of t he populat ion densit y f unct ion obt ained f rom perf ect ly mixed cont inuous cryst allizers; unf ort unat ely,
such behavior cannot be used t o dist inguish bet ween size-dependent growt h and growt h rat e dispersion, as bot h have t he same qualit at ive
ef f ect s on populat ion densit y.
Size-dependent Crystal Growth. A number of empirical expressions correlat e t he apparent ef f ect of cryst al size on growt h
rat e (30). The most commonly used correlat ion uses t hree empirical paramet ers t o correlat e growt h rat e wit h cryst al size:
G = G
0
(1+ L)
b
; b < 1
(29)
where G
0
, , and b are det ermined f rom experiment al dat a. There have been at t empt s t o relat e t he kinet ic paramet er bt o cryst allizer
variables; t he only success in t his regard (31) showed a qualit at ive dependence on cryst allizer volume. Several t heories have been proposed
t o explain size-dependent growt h kinet ics, but none has been subst ant iat ed by direct observat ion or used t o predict t he onset of such
behavior. One explanat ion seems part icularly appealing: larger cryst als impact impellers and ot her cryst allizer int ernals wit h higher
f requency and energy t han smaller cryst als; t heref ore, t he larger cryst als are recipient s of more surf ace breaks and irregularit ies t hat lead t o
higher growt h rat es.
Growth Rate D ispersion. This phenomenon is t he exhibit ion of dif f erent growt h rat es by cryst als in a magma, even t hough
t hey may have t he same size and are exposed t o ident ical condit ions. I t is now generally accept ed t hat many observat ions originally
at t ribut ed t o size-dependent growt h were due t o growt h rat e dispersion. Such erroneous int erpret at ions were t he result of similarit ies in t he
ef f ect s of t he t wo t ypes of behavior on cryst al size dist ribut ions.
The ef f ect s of growt h rat e dispersion on a populat ion of sucrose cryst als were f irst charact erized by a linear correlat ion of t he
variance of t he populat ion about a mean size L wit h t he ext ent of growt h (30). I t was demonst rat ed lat er (32,33) t hat growt h rat e dispersion
could account f or anomalous charact erist ics in t he populat ion densit y of cryst als obt ained f rom cont inuous, st eady-st at e cryst allizers. L at er
st udies examined bat ch cryst allizat ion dat a t o show t hat apparent size-dependent growt h of pot assium alum cryst als was a manif est at ion of
growt h rat e dispersion (34). Cryst als of cit ric acid monohydrat e generat ed by cont act nucleat ion were f ound t o exhibit growt h rat e
dispersion but not size-dependent growt h (35).
Two dist inct ly dif f erent mechanisms leading t o growt h rat e dispersion have experiment al support . The f irst assumes t hat all cryst als
have t he same t ime-averaged growt h rat e, but t he growt h rat es of individual cryst als f luct uat e about some mean value (36). D irect evidence
of random f luct uat ions in growt h rat es has been report ed f or magnesium sulf at e hept ahydrat e (37) and pot assium alum (38). The second
assumes t hat cryst als are f ormed wit h a charact erist ic dist ribut ion of growt h rat es, but individual cryst als ret ain a const ant growt h rat e
t hroughout t heir residence in a cryst allizer. Findings on cit ric acid (35), pot assium nit rat e (39), and ammonium dihydrogen phosphat e (40)
support t his mechanism.
Surf ace int egrat ion is t hought t o be t he primary f act or in bot h mechanisms of growt h rat e dispersion. The BCF t heory indicat es t hat
t he growt h rat e of a cryst al f ace depends on t he number, sign, and locat ion of screw dislocat ions on t he surf ace of a growing cryst al.
Collisions of cryst als wit h each ot her and cryst allizer int ernals result in changes in t he dislocat i on net work of a cryst al, t hereby leading t o
random f luct uat ions of growt h rat es. Changes in t he dislocat ion net works also occur simply due t o t he imperf ect growt h of cryst al f aces. A
dist ribut ion of growt h rat es is a result of t he varying dislocat ion net works and densit ies among nuclei and seed cryst als.
Alt hough evidence exist s f or bot h mechanisms of growt h rat e dispersion, separat e mat hemat ical models were developed f or
incorporat ing t he t wo mechanisms int o descript ions of cryst al populat ions: random growt h rat e f luct uat ions (36) and growt h rat e
dist ribut ions (33,40). Bot h mechanisms can be included in a populat ion balance t o show t he relat ive ef f ect s of t he t wo mechanisms on
cryst al size dist ribut ions f rom bat ch and cont inuous cryst allizers (41).
Crystal Characteristics
The morphology (including cryst al shape or habit ), size dist ribut ion, and purit y of cryst alline mat erials can det ermine t he success in f ulf illing
t he f unct ion of a cryst allizat ion operat ion.
M orphology. A cryst al is highly organized, and const it uent unit s, which can be at oms, molecules, or ions, are posit ioned in a
t hree-dimensional periodic pat t ern called a space lat t ice. A charact erist ic cryst al shape result s f r om t he regular int ernal st ruct ure of t he solid
wit h cryst al surf aces f orming parallel t o planes f ormed by t he const it uent unit s. The surf aces (f aces) of a cryst al may exhibit varying degrees
of development , wit h a concomit ant variat ion in macroscopic appearance.
I f at oms, molecules, or ions of a unit cell are t reat ed as point s, t he lat t ice st ruct ure of t he ent i re cryst al can be shown t o be a
mult iplicat ion in t hree dimensions of t he unit cell. Only 14 possible lat t ices (called Bravais lat t i ces) can be drawn in t hree dimensions. These
can be classif ied int o seven groups based on t heir element s of symmet ry. Moreover, examinat ion of t he element s of symmet ry (about a
point , a line, or a plane) f or a cryst al shows t hat t here are 32 dif f erent combinat ions (classes) t hat can be grouped int o seven syst ems. The
correspondence of t hese seven syst ems t o t he seven lat t ice groups is shown in Table 1.
CRYSTALLIZATION Vol 7
Kirk-Othmer Encyclopedia of Chemical Technology (4th Edition) 12
T able 1. T he 14 Bravais Lattices
a
Type of symmet ry L at t ice Cryst al syst em
cubic cube regular
body-cent ered cube
f ace-cent ered cube
t et ragonal square prism t et ragonal
body-cent ered square prism
ort horhombic rect angular prism ort horhombic
body-cent ered rect angular prism
rhombic prism
body-cent ered rhombic prism
monoclinic monoclinic parallelepiped monoclinic
clinorhombic
t riclinic t riclinic parallelepiped t riclinic
rhomboidal rhombohedron t riclinic
hexagonal hexagonal prism hexagonal
a
Ref . 5.
The general shape of a cryst al is ref erred t o as it s habit . The appearance of t he cryst alline product and it s processing charact erist ics
(such as washing and f ilt rat ion) are af f ect ed by cryst al habit . Relat ive growt h rat es of t he f aces of a cryst al det ermine it s shape;
f ast er-growing f aces become smaller t han slower-growing f aces and, in t he ext reme, may disappear f rom t he cryst al alt oget her. Growt h
rat es depend on t he presence of impurit ies, rat es of cooling, t emperat ure, solvent , mixing, and supersat urat ion. Furt hermore, t he
import ance of each of t hese f act ors may vary f rom one cryst al f ace t o anot her. For example, consider Figure 9 which shows t hat t he (111,
f ace grows bet ween 1.6 and 2.2 t imes as f ast as t he (110, f ace at t he condit ions examined. These result s account f or t he elongat ed cryst al
shape exhibit ed by magnesium sulf at e hept ahydrat e cryst als. I n addit ion, t he ef f ect s of supersat urat ion and t emperat ure are dif f erent on t he
growt h rat es of t he t wo f aces st udied. Such behavior leads t o changes in habit as t he t emperat ure and/ or supersat urat ion are changed in a
cryst allizer.
Fig. 9. Growt h rat e of f aces of MgSO
4
7H
2
O. " , < 111 > f ace at T
sat
= 38:0

C; , < 111 > f ace at T


sat
= 35:5

C; , < 110 > f ace at


T
sat
= 38:0

C; & , < 110 > f ace at T


sat
= 33:5

C; solut ion velocity = 1:2 cm=s (42). Reprint ed wit h permission of t he American Chemical
Societ y.
A number of st udies have shown t hat various addit ives can be included in a process st ream t o alt er cryst al habit (5). Predict ion of
such behavior is dif f icult and ext ensive laborat ory or bench-scale experiment s may be required t o evaluat e t he ef f ect iveness of habit
modif iers. More recent ly, some measure of success has been achieved wit h alt ering t he habit of organic cryst als based on t he molecular
st ruct ure and charact erist ics of t he cryst allizing species. One cat egory of addit ives af f ect ing cryst al habit is surf act ant s (43). Should an
T able 1. T he 14 Bravais Lattices
a
Type of symmet ry L at t ice Cryst al syst em
cubic cube regular
body-cent ered cube
f ace-cent ered cube
t et ragonal square prism t et ragonal
body-cent ered square prism
ort horhombic rect angular prism ort horhombic
body-cent ered rect angular prism
rhombic prism
body-cent ered rhombic prism
monoclinic monoclinic parallelepiped monoclinic
clinorhombic
t riclinic t riclinic parallelepiped t riclinic
rhomboidal rhombohedron t riclinic
hexagonal hexagonal prism hexagonal
a
Ref . 5.
The general shape of a cryst al is ref erred t o as it s habit . The appearance of t he cryst alline product and it s processing charact erist ics
(such as washing and f ilt rat ion) are af f ect ed by cryst al habit . Relat ive growt h rat es of t he f aces of a cryst al det ermine it s shape;
f ast er-growing f aces become smaller t han slower-growing f aces and, in t he ext reme, may disappear f rom t he cryst al alt oget her. Growt h
rat es depend on t he presence of impurit ies, rat es of cooling, t emperat ure, solvent , mixing, and supersat urat ion. Furt hermore, t he
import ance of each of t hese f act ors may vary f rom one cryst al f ace t o anot her. For example, consider Figure 9 which shows t hat t he (111,
f ace grows bet ween 1.6 and 2.2 t imes as f ast as t he (110, f ace at t he condit ions examined. These result s account f or t he elongat ed cryst al
shape exhibit ed by magnesium sulf at e hept ahydrat e cryst als. I n addit ion, t he ef f ect s of supersat urat ion and t emperat ure are dif f erent on t he
growt h rat es of t he t wo f aces st udied. Such behavior leads t o changes in habit as t he t emperat ure and/ or supersat urat ion are changed in a
cryst allizer.
Fig. 9. Growt h rat e of f aces of MgSO
4
7H
2
O. " , < 111 > f ace at T
sat
= 38:0

C; , < 111 > f ace at T


sat
= 35:5

C; , < 110 > f ace at


T
sat
= 38:0

C; & , < 110 > f ace at T


sat
= 33:5

C; solut ion velocity = 1:2 cm=s (42). Reprint ed wit h permission of t he American Chemical
Societ y.
A number of st udies have shown t hat various addit ives can be included in a process st ream t o alt er cryst al habit (5). Predict ion of
such behavior is dif f icult and ext ensive laborat ory or bench-scale experiment s may be required t o evaluat e t he ef f ect iveness of habit
modif iers. More recent ly, some measure of success has been achieved wit h alt ering t he habit of organic cryst als based on t he molecular
st ruct ure and charact erist ics of t he cryst allizing species. One cat egory of addit ives af f ect ing cryst al habit is surf act ant s (43). Should an
CRYSTALLIZATION Vol 7
Kirk-Othmer Encyclopedia of Chemical Technology (4th Edition) 13
addit ive enhance t he propert ies of a cryst alline mat erial, f or example, by making it easier t o f ilt er, t he expense associat ed wit h it s use may be
warrant ed. Signif icant ef f ort s t oward t ailoring addit ives so t hat t hey have specif ic ef f ect s on cryst al habit have been made by a number of
research groups (44,45).
Pol ymorphi sm is a condit ion in which a specif ic chemical subst ance may cryst allize int o dif f erent f orms. For example, ammonium
nit rat e exhibit s f our changes in f orm (5) bet ween 18

and 125C:
Transit ions f rom one polymorphic f orm t o anot her may be accompanied by changes in specif ic volume, which may lead t o dest ruct ion of
t he cryst al and cont ainers in which t he subst ance is st ored.
A specif ic polymorph may be absolut ely essent ial f or a cryst alline product , f or example, one polymor ph may have a more desirable
color or great er hardness or disperse in wat er more easily t han anot her polymorph. Of t en, one polymorphic f orm is more st able t han
anot her (f or example, at 80C t he ort horhombic I f orm of ammonium nit rat e is more st able t han t he t rigonal f orm) at condit ions t o which
a product is exposed. An int erest ing approach t o keeping a less st able polymorph f rom t ransf orming t o a more st able, but less desireable,
polymorphic f orm uses an addit ive t o block rearrangement of t he molecular st ruct ure leading t o t he undesired f orm (46).
Agglomeration. Many of t he analyses of indust rial cryst allizers require t hat t he part icle recovered f rom t he cryst allizer consist of
a single cryst al. I t is only wit h t his t ype of syst em t hat single growt h rat es are likely t o be exhi bit ed and, moreover, many of t he propert ies of
t he cryst al are af f ect ed delet eriously by agglomerat ion. Purit y, f or example, t ypically is diminished when agglomerat ion occurs. Count ering
t he negat ive aspect s of agglomerat ion is recognit ion t hat in many syst ems t he single cryst als produced by normal cryst al growt h would be
t oo small t o be separable using convent ional solidliquid separat ion equipment . I n such inst ances, t here would be no product wit hout
agglomerat ion.
The needs associat ed wit h a great er underst anding of agglomerat ion f all int o at least t wo separat e areas: ident if ying t he variables
af f ect ing agglomerat ion and account ing properly f or agglomerat ion in a populat ion balance around a cryst allizer. The lat t er of t hese has
been addressed (47,48), but t he subject mat t er is considered beyond t he scope of t he present discussion.
Several process variables t hat inf luence agglomerat ion of copper sulf at e pent ahydrat e [ 7758-99-8] cryst als have been ident if ied (49).
Part icles originally appearing t o be single cryst als were f ound t o be agglomerat es of complex st ruct ure. Elect ron phot omicrographs showed
t hat t he agglomerat es were f ormed early in t he lif e of cryst als comprising t he agglomerat es and t hat t he growt h of t hese agglomerat es had
f ollowed a complex and unpredict able pat t ern. The percent ages of agglomerat es in t he part icles recovered f rom a series of
mixed-suspension, mixed-product experiment s were f ound t o increase wit h increasing supersat urat ion, increasing magma densit y, and
decreasing agit at ion. The observat ions f it wit h a hypot hesis t hat t he agglomerat ion result ed when t wo or more cryst als came t oget her and
were bonded t hrough overgrowt h of cont act areas. Such a hypot hesis is inadequat e, however, in predict ing when agglomerat ion will occur
and t he key variables t hat can be adjust ed t o cont rol t he agglomerat ion.
Purity. Alt hough cryst allizat ion has been employed ext ensively as a separat ion process, purif icat ion t echniques using
cryst allizat ion have become increasing import ant . Mechanisms by which impurit ies can be incorporat ed int o cryst alline product s include
adsorpt ion of impurit ies on cryst al surf aces (50), solvent ent rapment in cracks, crevices and agglomerat es, and inclusion of pocket s of liquid
(51). An impurit y having a st ruct ure suf f icient ly similar t o t he mat erial being cryst allized can also be incorporat ed int o t he cryst al lat t ice by
subst it ut ion or ent rapment (52,53). Among t hese mechanisms, inclusion f ormat ion has been ext ensively st udied (5458). I t has also been
suggest ed t hat t he purit y may be direct ly linked t o size and habit of product cryst als, but t he int eract ion does not appear t o be simple. I t has
been not ed (59) t hat t he key t o producing high purit y cryst als was t o maint ain t he supersat urat ion at a low level so t hat large cryst als were
obt ained. Ot hers have f ound t hat reducing t he size of ammonium perchlorat e cryst als result ed in a subst ant ial decrease in moist ure due t o
inclusion (58).
K ey f act ors in solving problems associat ed wit h cryst al purit y are t he locat ion, ie, on t he surf ace or incorporat ed in t he cryst al, and
t he nat ure of t he impurit y. I mpurit ies are on t he ext erior of host cryst als as a result of adsorpt ion; wet t ing by a solvent t hat cont ains t he
impurit ies; or ent rapment of impure solvent in cracks, crevices, agglomerat es, and aggregat es. I ncor porat ion of impurit ies wit hin cryst als
comes about t hrough f ormat ion of inclusions (also ref erred t o as occlusions) of solvent , lat t ice subst it ut ion, or lat t ice ent rapment .
Obviously, t he charact erist ics of an impurit y det ermine whet her it is posit ioned on t he surf ace or t he int erior of host cryst als. Three key
impurit y t ypes are solut es similar t o t he product , solut es dissimilar f rom t he product , and t he solvent . The ef f ect s of process variables on
t he purit y of L -isoleucine cryst allized f rom aqueous solut ions cont aining ot her amino acids (impurit ies) have been det ermined (60). Anot her
st udy has examined how t he met hanol cont ent of L -serine cryst als could be minimized when t he mode of cryst allizat ion is addit ion of
met hanol t o sat urat ed aqueous solut ions (4). Mixing and t he rat e at which supersat urat ion is generat ed are import ant in bot h of t hese
cases.
Crystal Size D istributions. Part iculat e mat t er produced by cryst allizat ion has a dist ribut ion of sizes t hat varies in a def init e
way over a specif ic size range. A cryst al size dist ribut ion (CSD ) is most commonly expressed as a populat ion (number) dist ribut ion relat ing
addit ive enhance t he propert ies of a cryst alline mat erial, f or example, by making it easier t o f ilt er, t he expense associat ed wit h it s use may be
warrant ed. Signif icant ef f ort s t oward t ailoring addit ives so t hat t hey have specif ic ef f ect s on cryst al habit have been made by a number of
research groups (44,45).
Pol ymorphi sm is a condit ion in which a specif ic chemical subst ance may cryst allize int o dif f erent f orms. For example, ammonium
nit rat e exhibit s f our changes in f orm (5) bet ween 18

and 125C:
Transit ions f rom one polymorphic f orm t o anot her may be accompanied by changes in specif ic volume, which may lead t o dest ruct ion of
t he cryst al and cont ainers in which t he subst ance is st ored.
A specif ic polymorph may be absolut ely essent ial f or a cryst alline product , f or example, one polymor ph may have a more desirable
color or great er hardness or disperse in wat er more easily t han anot her polymorph. Of t en, one polymorphic f orm is more st able t han
anot her (f or example, at 80C t he ort horhombic I f orm of ammonium nit rat e is more st able t han t he t rigonal f orm) at condit ions t o which
a product is exposed. An int erest ing approach t o keeping a less st able polymorph f rom t ransf orming t o a more st able, but less desireable,
polymorphic f orm uses an addit ive t o block rearrangement of t he molecular st ruct ure leading t o t he undesired f orm (46).
Agglomeration. Many of t he analyses of indust rial cryst allizers require t hat t he part icle recovered f rom t he cryst allizer consist of
a single cryst al. I t is only wit h t his t ype of syst em t hat single growt h rat es are likely t o be exhi bit ed and, moreover, many of t he propert ies of
t he cryst al are af f ect ed delet eriously by agglomerat ion. Purit y, f or example, t ypically is diminished when agglomerat ion occurs. Count ering
t he negat ive aspect s of agglomerat ion is recognit ion t hat in many syst ems t he single cryst als produced by normal cryst al growt h would be
t oo small t o be separable using convent ional solidliquid separat ion equipment . I n such inst ances, t here would be no product wit hout
agglomerat ion.
The needs associat ed wit h a great er underst anding of agglomerat ion f all int o at least t wo separat e areas: ident if ying t he variables
af f ect ing agglomerat ion and account ing properly f or agglomerat ion in a populat ion balance around a cryst allizer. The lat t er of t hese has
been addressed (47,48), but t he subject mat t er is considered beyond t he scope of t he present discussion.
Several process variables t hat inf luence agglomerat ion of copper sulf at e pent ahydrat e [ 7758-99-8] cryst als have been ident if ied (49).
Part icles originally appearing t o be single cryst als were f ound t o be agglomerat es of complex st ruct ure. Elect ron phot omicrographs showed
t hat t he agglomerat es were f ormed early in t he lif e of cryst als comprising t he agglomerat es and t hat t he growt h of t hese agglomerat es had
f ollowed a complex and unpredict able pat t ern. The percent ages of agglomerat es in t he part icles recovered f rom a series of
mixed-suspension, mixed-product experiment s were f ound t o increase wit h increasing supersat urat ion, increasing magma densit y, and
decreasing agit at ion. The observat ions f it wit h a hypot hesis t hat t he agglomerat ion result ed when t wo or more cryst als came t oget her and
were bonded t hrough overgrowt h of cont act areas. Such a hypot hesis is inadequat e, however, in predict ing when agglomerat ion will occur
and t he key variables t hat can be adjust ed t o cont rol t he agglomerat ion.
Purity. Alt hough cryst allizat ion has been employed ext ensively as a separat ion process, purif icat ion t echniques using
cryst allizat ion have become increasing import ant . Mechanisms by which impurit ies can be incorporat ed int o cryst alline product s include
adsorpt ion of impurit ies on cryst al surf aces (50), solvent ent rapment in cracks, crevices and agglomerat es, and inclusion of pocket s of liquid
(51). An impurit y having a st ruct ure suf f icient ly similar t o t he mat erial being cryst allized can also be incorporat ed int o t he cryst al lat t ice by
subst it ut ion or ent rapment (52,53). Among t hese mechanisms, inclusion f ormat ion has been ext ensively st udied (5458). I t has also been
suggest ed t hat t he purit y may be direct ly linked t o size and habit of product cryst als, but t he int eract ion does not appear t o be simple. I t has
been not ed (59) t hat t he key t o producing high purit y cryst als was t o maint ain t he supersat urat ion at a low level so t hat large cryst als were
obt ained. Ot hers have f ound t hat reducing t he size of ammonium perchlorat e cryst als result ed in a subst ant ial decrease in moist ure due t o
inclusion (58).
K ey f act ors in solving problems associat ed wit h cryst al purit y are t he locat ion, ie, on t he surf ace or incorporat ed in t he cryst al, and
t he nat ure of t he impurit y. I mpurit ies are on t he ext erior of host cryst als as a result of adsorpt ion; wet t ing by a solvent t hat cont ains t he
impurit ies; or ent rapment of impure solvent in cracks, crevices, agglomerat es, and aggregat es. I ncor porat ion of impurit ies wit hin cryst als
comes about t hrough f ormat ion of inclusions (also ref erred t o as occlusions) of solvent , lat t ice subst it ut ion, or lat t ice ent rapment .
Obviously, t he charact erist ics of an impurit y det ermine whet her it is posit ioned on t he surf ace or t he int erior of host cryst als. Three key
impurit y t ypes are solut es similar t o t he product , solut es dissimilar f rom t he product , and t he solvent . The ef f ect s of process variables on
t he purit y of L -isoleucine cryst allized f rom aqueous solut ions cont aining ot her amino acids (impurit ies) have been det ermined (60). Anot her
st udy has examined how t he met hanol cont ent of L -serine cryst als could be minimized when t he mode of cryst allizat ion is addit ion of
met hanol t o sat urat ed aqueous solut ions (4). Mixing and t he rat e at which supersat urat ion is generat ed are import ant in bot h of t hese
cases.
Crystal Size D istributions. Part iculat e mat t er produced by cryst allizat ion has a dist ribut ion of sizes t hat varies in a def init e
way over a specif ic size range. A cryst al size dist ribut ion (CSD ) is most commonly expressed as a populat ion (number) dist ribut ion relat ing
CRYSTALLIZATION Vol 7
Kirk-Othmer Encyclopedia of Chemical Technology (4th Edition) 14
t he number of cryst als at each size t o t he size or as a mass (weight ) dist ribut ion expressing how mass is dist ribut ed over t he size range. The
t wo dist ribut ions are relat ed and af f ect many aspect s of cryst al processing and propert ies, including appearance, solidseparat ion, purit y,
react ions, dissolut ion, and ot her propert ies involving surf ace area.
Populat ion densit y (n) has dimensions number/ (volume)(lengt h); it is a key quant it y in t he discussion of CSD , a f unct ion of t he
charact erist ic cryst al dimension L , and it is def ined so t hat it is independent of t he magnit ude of t he syst em. When a t ot al populat ion
densit y is used, t he symbol is n and t he unit s are number/ lengt h. Populat ion densit y is def ined by let t ing AN be t he number of cryst als per
unit syst em volume in a size range f rom L t o L + L, so t hat
n =
limit
L ! 0
N
L
(30)
The arbit rary syst em volume on which n is based must be def ined bef ore t he populat ion densit y f unct ion has meaning. For example, t he
volume may be t hat of t he slurry or t he clear liquor in t he syst em.
The f unct ion N in equat ion 30 is a cumulat ive number dist ribut ion represent ing t he number of cryst als per unit volume in t he
dist ribut ion t hat have a charact erist ic dimension less t han L '. Theref ore,
N( L
0
) =
Z
L
0
0
ndL
(31)
and t he f ract ion of t he cryst als in t he dist ribut ion F (L ') t hat have a size less t han L ' can be calculat ed as
F( L
0
) =
N( L
0
)
N
t ot
(32)
A mass (weight ) densit y f unct ion, given t he symbol m and having dimensions mass/ (volume)(lengt h), can be def ined analogously t o
populat ion densit y; let t ing AM be t he mass of cryst als per unit syst em volume in t he size range L t o L + L,
m =
limit
L ! 0
M
L
(33)
The t wo densit y f unct ions can be relat ed t hrough a simple shape f act or as f ollows. Suppose t he mass of a single cryst al is M
c
and t he
charact erist ic dimension of t hat cryst al is L . I f t he cryst al is f rom a populat ion in which shape is not a f unct ion of size, t hen t he mass of any
cryst al f rom t hat populat ion is relat ed t o charact erist ic dimension by a volume shape f act or:
M
c
= k
v
L
3
(34)
Recognizing t hat t he mass of cryst als in a sample is t he product of t he number of cryst als and t he mass of a single cryst al, mass and
populat ion densit ies may be relat ed by t he expression
M = k
v
L
3
N
(35)
where p is cryst al densit y. D ividing by AL and t aking t he limit as t his quant it y approaches zero,
m = k
v
L
3
n
(36)
The f unct ion M used in t he above equat ions is a cumulat ive mass dist ribut ion f unct ion, represent ing t he mass of cr yst als having a
charact erist ic dimension less t han L '. The t ot al mass of cryst als per unit volume is relat ed t o populat ion densit y by t he equat ion
M
T
= k
v

Z
1
0
L
3
ndL
(37)
This quant it y, which is of t en ref erred t o as magma densit y or solids concent rat ion (mass of cryst als per unit syst em volume), is of t en an
import ant process variable. A cumulat ive mass f ract ion of cryst als having a size less t han L ' can also be def ined as
t he number of cryst als at each size t o t he size or as a mass (weight ) dist ribut ion expressing how mass is dist ribut ed over t he size range. The
t wo dist ribut ions are relat ed and af f ect many aspect s of cryst al processing and propert ies, including appearance, solidseparat ion, purit y,
react ions, dissolut ion, and ot her propert ies involving surf ace area.
Populat ion densit y (n) has dimensions number/ (volume)(lengt h); it is a key quant it y in t he discussion of CSD , a f unct ion of t he
charact erist ic cryst al dimension L , and it is def ined so t hat it is independent of t he magnit ude of t he syst em. When a t ot al populat ion
densit y is used, t he symbol is n and t he unit s are number/ lengt h. Populat ion densit y is def ined by let t ing AN be t he number of cryst als per
unit syst em volume in a size range f rom L t o L + L, so t hat
n =
limit
L ! 0
N
L
(30)
The arbit rary syst em volume on which n is based must be def ined bef ore t he populat ion densit y f unct ion has meaning. For example, t he
volume may be t hat of t he slurry or t he clear liquor in t he syst em.
The f unct ion N in equat ion 30 is a cumulat ive number dist ribut ion represent ing t he number of cryst als per unit volume in t he
dist ribut ion t hat have a charact erist ic dimension less t han L '. Theref ore,
N( L
0
) =
Z
L
0
0
ndL
(31)
and t he f ract ion of t he cryst als in t he dist ribut ion F (L ') t hat have a size less t han L ' can be calculat ed as
F( L
0
) =
N( L
0
)
N
t ot
(32)
A mass (weight ) densit y f unct ion, given t he symbol m and having dimensions mass/ (volume)(lengt h), can be def ined analogously t o
populat ion densit y; let t ing AM be t he mass of cryst als per unit syst em volume in t he size range L t o L + L,
m =
limit
L ! 0
M
L
(33)
The t wo densit y f unct ions can be relat ed t hrough a simple shape f act or as f ollows. Suppose t he mass of a single cryst al is M
c
and t he
charact erist ic dimension of t hat cryst al is L . I f t he cryst al is f rom a populat ion in which shape is not a f unct ion of size, t hen t he mass of any
cryst al f rom t hat populat ion is relat ed t o charact erist ic dimension by a volume shape f act or:
M
c
= k
v
L
3
(34)
Recognizing t hat t he mass of cryst als in a sample is t he product of t he number of cryst als and t he mass of a single cryst al, mass and
populat ion densit ies may be relat ed by t he expression
M = k
v
L
3
N
(35)
where p is cryst al densit y. D ividing by AL and t aking t he limit as t his quant it y approaches zero,
m = k
v
L
3
n
(36)
The f unct ion M used in t he above equat ions is a cumulat ive mass dist ribut ion f unct ion, represent ing t he mass of cr yst als having a
charact erist ic dimension less t han L '. The t ot al mass of cryst als per unit volume is relat ed t o populat ion densit y by t he equat ion
M
T
= k
v

Z
1
0
L
3
ndL
(37)
This quant it y, which is of t en ref erred t o as magma densit y or solids concent rat ion (mass of cryst als per unit syst em volume), is of t en an
import ant process variable. A cumulat ive mass f ract ion of cryst als having a size less t han L ' can also be def ined as
CRYSTALLIZATION Vol 7
Kirk-Othmer Encyclopedia of Chemical Technology (4th Edition) 15
W( L
0
) =
M ( L
0
)
M
T
=
k
v

R
L
0
0
L
3
n(L) dL
M
T
(38)
M oments of a dist ribut ion of t en provide inf ormat ion t hat can be used t o charact erize part iculat e mat t er. The j t h moment of t he
populat ion densit y f unct ion n is def ined as
m
j
= j t h moment =
Z
1
0
L
j
n dL
(39)
I t can be demonst rat ed t hat t he t ot al number of cryst als, t he t ot al lengt h, t he t ot al area, and t he t ot al volume of cryst als, all in a unit of
syst em volume, can be evaluat ed f rom t he zero, f irst , second, and t hird moment s of t he populat ion densit y f unct ion.
An average cryst al size can be used t o charact erize a CSD . However, t he average can be det ermined on any of several bases, and t he
basis select ed must be specif ied f or t he average t o be usef ul. More t han 20 dif f erent averaging procedures have been proposed, yet none is
generally sat isf act ory or pref erred (5).
The complet e charact erizat ion of a part iculat e mat erial requires development of a f unct ional relat ionship bet ween cryst al size and
populat ion or mass. The f unct ional relat ionship may assume an analyt ical f orm (7), but more f requent ly it is necessary t o work wit h dat a
t hat do not f it such expressions. As such det ail may be cumbersome or unavailable f or a cryst alline product , t he mat erial may be more
simply (and less complet ely) described in t erms of a single cryst al size and a spread of t he dist ribut ion about t hat specif ied dimension.
The dominant cryst al size, L
D
, is most of t en used as a represent at ion of t he product size, because it represent s t he size about which
most of t he mass in t he dist ribut ion is clust ered. I f t he mass densit y f unct ion def ined in equat ion 33 is plot t ed f or a set of hypot het ical dat a
as shown in Figure 10, it would t ypically be observed t o have a maximum at t he dominant cryst al size. I n ot her words, t he dominant cryst al
size L
D
is t hat charact erist ic cryst al dimension at which dm=dL = 0. Also shown in Figure 10 is t he t heoret ical result obt ained when t he
mass densit y is det ermined f or a perf ect ly mixed, cont inuous cryst allizer wit hin which invariant cryst al growt h occurs. That is, mass densit y
is f ound f or such syst ems t o f ollow a relat ionship of t he f orm m = aL
3
exp ( bL), where a and b are syst em-dependent paramet ers.
Fig. 10. D et erminat ion L
D
f rom plot of mass densit y f unct ion.
The coef f icient of variat ion (cv) of a dist ribut ion is a measure of t he spread of t he dist ribut ion about some charact erist ic size. I t is
of t en used in conjunct ion wit h dominant size t o charact erize cryst al populat ions t hrough t he equat ion
cv =

L
D
(40)
where is t he st andard deviat ion of t he dist ribut ion. The coef f icient of variat ion of t he mass densit y f unct ion about t he dominant cryst al
size is given by
cv =

m
3
m
5
m
2
4
1

1=2
(41)
W( L
0
) =
M ( L
0
)
M
T
=
k
v

R
L
0
0
L
3
n(L) dL
M
T
(38)
M oments of a dist ribut ion of t en provide inf ormat ion t hat can be used t o charact erize part iculat e mat t er. The j t h moment of t he
populat ion densit y f unct ion n is def ined as
m
j
= j t h moment =
Z
1
0
L
j
n dL
(39)
I t can be demonst rat ed t hat t he t ot al number of cryst als, t he t ot al lengt h, t he t ot al area, and t he t ot al volume of cryst als, all in a unit of
syst em volume, can be evaluat ed f rom t he zero, f irst , second, and t hird moment s of t he populat ion densit y f unct ion.
An average cryst al size can be used t o charact erize a CSD . However, t he average can be det ermined on any of several bases, and t he
basis select ed must be specif ied f or t he average t o be usef ul. More t han 20 dif f erent averaging procedures have been proposed, yet none is
generally sat isf act ory or pref erred (5).
The complet e charact erizat ion of a part iculat e mat erial requires development of a f unct ional relat ionship bet ween cryst al size and
populat ion or mass. The f unct ional relat ionship may assume an analyt ical f orm (7), but more f requent ly it is necessary t o work wit h dat a
t hat do not f it such expressions. As such det ail may be cumbersome or unavailable f or a cryst alline product , t he mat erial may be more
simply (and less complet ely) described in t erms of a single cryst al size and a spread of t he dist ribut ion about t hat specif ied dimension.
The dominant cryst al size, L
D
, is most of t en used as a represent at ion of t he product size, because it represent s t he size about which
most of t he mass in t he dist ribut ion is clust ered. I f t he mass densit y f unct ion def ined in equat ion 33 is plot t ed f or a set of hypot het ical dat a
as shown in Figure 10, it would t ypically be observed t o have a maximum at t he dominant cryst al size. I n ot her words, t he dominant cryst al
size L
D
is t hat charact erist ic cryst al dimension at which dm=dL = 0. Also shown in Figure 10 is t he t heoret ical result obt ained when t he
mass densit y is det ermined f or a perf ect ly mixed, cont inuous cryst allizer wit hin which invariant cryst al growt h occurs. That is, mass densit y
is f ound f or such syst ems t o f ollow a relat ionship of t he f orm m = aL
3
exp ( bL), where a and b are syst em-dependent paramet ers.
Fig. 10. D et erminat ion L
D
f rom plot of mass densit y f unct ion.
The coef f icient of variat ion (cv) of a dist ribut ion is a measure of t he spread of t he dist ribut ion about some charact erist ic size. I t is
of t en used in conjunct ion wit h dominant size t o charact erize cryst al populat ions t hrough t he equat ion
cv =

L
D
(40)
where is t he st andard deviat ion of t he dist ribut ion. The coef f icient of variat ion of t he mass densit y f unct ion about t he dominant cryst al
size is given by
cv =

m
3
m
5
m
2
4
1

1=2
(41)
CRYSTALLIZATION Vol 7
Kirk-Othmer Encyclopedia of Chemical Technology (4th Edition) 16
Population Balances and Crystal Size D istributions
Populat ion balances and cryst allizat ion kinet ics may be used t o relat e process variables t o t he cryst al size dist ribut ion produced by t he
cryst allizer. Such balances are coupled t o t he more f amiliar balances on mass and energy. I t is assumed t hat t he populat ion dist ribut ion is a
cont inuous f unct ion and t hat cryst al size, surf ace area, and volume can be described by a charact eri st ic dimension L . Area and volume
shape f act ors are assumed t o be const ant , which is t o say t hat t he morphology of t he cryst al does not change wit h size.
A balance is f ormulat ed around a cont rol volume V
T
on t he number of cryst als in any size range, say L
1
t o L
2
. I t must account f or
cryst als t hat ent er and leave t he size range by convect ive f low and cryst als t hat ent er and leave t he size range by cryst al growt h. Cryst al
breakage and agglomerat ion are assumed t o be negligible in t he present analysis, and it is assumed t hat cryst als are f ormed by nucleat ion at
size zero. The rat e of cryst al growt h G is def ined as t he rat e of change of t he charact erist ic cryst al dimension L ; t hat is, G = dL=dt .
Consider t he cryst allizer shown in Figure 11. I f it is assumed t hat t he cryst allizer is well mixed wit h a const ant slurry volume V
T
, t hen,
as shown (7), t he f ollowing part ial dif f erent ial populat ion balance can be derived:
@(nG)
@L
+
Q
0
n
V
T

Q
i
n
i
V
T
=
@n
@t
(42)
Fig. 11. Schemat ic diagram of a simple, perf ect ly mixed cryst allizer.
I f t he cryst allizer is now assumed t o operat e wit h a clear f eed ( n
i
= 0), at st eady st at e (@n=@t = 0), and if t he cryst al growt h rat e G is
invariant and a mean residence t ime t is def ined as V
T
/ Q
0
, t hen t he populat ion balance can be writ t en as
G
dn
dL
+
n

= 0
(43)
t is of t en ref erred t o as t he drawdown t ime t o ref lect t hat it is t he t ime required t o empt y t he cont ent s f rom t he cryst allizer if t he f eed is set
t o zero. Equat ion 43 can be int egrat ed using t he boundary condit ion n = n
0
at L = 0:
n = n
0
exp

L
G

(44)
I f t he magma volume V
T
is allowed t o vary in t he syst em on which equat ion 42 is based, t he populat ion balance becomes
@n
@t
+
@(nG)
@L
+ n
@(lnV
T
)
@t
+
Q
0
n
V
T
= 0
(45)
The cryst allizer model t hat led t o t he development of equat ions 44 and 45 is ref erred t o as t he mixed-suspension, mixed-product
removal (MSMPR) cryst allizer.
Population Balances and Crystal Size D istributions
Populat ion balances and cryst allizat ion kinet ics may be used t o relat e process variables t o t he cryst al size dist ribut ion produced by t he
cryst allizer. Such balances are coupled t o t he more f amiliar balances on mass and energy. I t is assumed t hat t he populat ion dist ribut ion is a
cont inuous f unct ion and t hat cryst al size, surf ace area, and volume can be described by a charact eri st ic dimension L . Area and volume
shape f act ors are assumed t o be const ant , which is t o say t hat t he morphology of t he cryst al does not change wit h size.
A balance is f ormulat ed around a cont rol volume V
T
on t he number of cryst als in any size range, say L
1
t o L
2
. I t must account f or
cryst als t hat ent er and leave t he size range by convect ive f low and cryst als t hat ent er and leave t he size range by cryst al growt h. Cryst al
breakage and agglomerat ion are assumed t o be negligible in t he present analysis, and it is assumed t hat cryst als are f ormed by nucleat ion at
size zero. The rat e of cryst al growt h G is def ined as t he rat e of change of t he charact erist ic cryst al dimension L ; t hat is, G = dL=dt .
Consider t he cryst allizer shown in Figure 11. I f it is assumed t hat t he cryst allizer is well mixed wit h a const ant slurry volume V
T
, t hen,
as shown (7), t he f ollowing part ial dif f erent ial populat ion balance can be derived:
@(nG)
@L
+
Q
0
n
V
T

Q
i
n
i
V
T
=
@n
@t
(42)
Fig. 11. Schemat ic diagram of a simple, perf ect ly mixed cryst allizer.
I f t he cryst allizer is now assumed t o operat e wit h a clear f eed ( n
i
= 0), at st eady st at e (@n=@t = 0), and if t he cryst al growt h rat e G is
invariant and a mean residence t ime t is def ined as V
T
/ Q
0
, t hen t he populat ion balance can be writ t en as
G
dn
dL
+
n

= 0
(43)
t is of t en ref erred t o as t he drawdown t ime t o ref lect t hat it is t he t ime required t o empt y t he cont ent s f rom t he cryst allizer if t he f eed is set
t o zero. Equat ion 43 can be int egrat ed using t he boundary condit ion n = n
0
at L = 0:
n = n
0
exp

L
G

(44)
I f t he magma volume V
T
is allowed t o vary in t he syst em on which equat ion 42 is based, t he populat ion balance becomes
@n
@t
+
@(nG)
@L
+ n
@(lnV
T
)
@t
+
Q
0
n
V
T
= 0
(45)
The cryst allizer model t hat led t o t he development of equat ions 44 and 45 is ref erred t o as t he mixed-suspension, mixed-product
removal (MSMPR) cryst allizer.
CRYSTALLIZATION Vol 7
Kirk-Othmer Encyclopedia of Chemical Technology (4th Edition) 17
D etermination of Crystallization Kinetics. Under st eady-st at e condit ions, t he t ot al number product ion rat e of cryst als in a
perf ect ly mixed cryst allizer is ident ical t o t he nucleat ion rat e, B
0
. Accordingly,
B
0
=
1

Z
1
0
ndL
(46)
For cryst allizers f ollowing t he const raint s leading t o equat ion 44,
B
0
= n
0
G
(47)
Combining equat ions 45 and 48
n =
B
0
G
exp

L
G

(48)
Analysis of equat ion 48 shows t hat a single sample t aken eit her f rom inside t he cryst allizer or f rom t he product st ream wil l allow evaluat ion
of nucleat ion and growt h rat es at t he syst em condit ions. Figure 12 shows a plot of t ypical populat ion densit y dat a obt ained f rom a
cryst allizer meet ing t he st at ed assumpt ions. The slope of t he plot of such dat a may be used t o obt ai n t he growt h rat e, and t he product of
t he int ercept and growt h rat e gives t he nucleat ion rat e.
Fig. 12. Plot of populat ion densit y as a f unct ion of size f or K N O
3
. = 15 min. For t he line, n = 16:528

exp ( 0:0090426L ); R = 0:99752;
slope = 1=G; int ercept = n
0
= B
0
=G.
Many indust rial cryst allizers operat e in a well-mixed or nearly well-mixed manner, and t he equat ions derived above can be used t o
describe t heir perf ormance. Furt hermore, t he simplicit y of t he equat ions describing an MSMPR cryst al lizer make experiment al equipment
conf igured t o meet t he assumpt ions leading t o equat ion 44 usef ul in det ermining nucleat ion and growt h kinet ics in syst ems of int erest .
From a series of runs at dif f erent operat ing condit ions, a correlat ion of nucleat ion and growt h kinet ics wit h appropriat e process
variables can be obt ained; t he result ing correlat ion can t hen be used t o guide eit her cryst allizer scaleup or t he development of an operat ing
st rat egy f or an exist ing cryst allizer. The variables af f ect ing nucleat ion and growt h kinet ics include t emperat ure, supersat urat ion, magma
densit y, and ext ernal st imuli, such as agit at ion or circulat ion rat e of t he magma. Empirical power-l aw f unct ions are used most f requent ly in
correlat ing nucleat ion and growt h rat es, but t he choice of t he independent variables can be just if ied f rom a mechanist ic perspect ive. For
example, syst ems t hat are believed t o f ollow secondary nucleat ion mechanisms should include a variable such as magma densit y t hat ref lect s
t he charact er of cryst als in t he cryst allizer. The most commonly used power-law f unct ions are
B
0
= k
1
s
b
M
j
T
(49)
G = k
2
s
g
(50)
I t is of t en dif f icult t o measure supersat urat ion, especially in syst ems t hat have high growt h rat es. Even t hough t he supersat urat ion in
D etermination of Crystallization Kinetics. Under st eady-st at e condit ions, t he t ot al number product ion rat e of cryst als in a
perf ect ly mixed cryst allizer is ident ical t o t he nucleat ion rat e, B
0
. Accordingly,
B
0
=
1

Z
1
0
ndL
(46)
For cryst allizers f ollowing t he const raint s leading t o equat ion 44,
B
0
= n
0
G
(47)
Combining equat ions 45 and 48
n =
B
0
G
exp

L
G

(48)
Analysis of equat ion 48 shows t hat a single sample t aken eit her f rom inside t he cryst allizer or f rom t he product st ream wil l allow evaluat ion
of nucleat ion and growt h rat es at t he syst em condit ions. Figure 12 shows a plot of t ypical populat ion densit y dat a obt ained f rom a
cryst allizer meet ing t he st at ed assumpt ions. The slope of t he plot of such dat a may be used t o obt ai n t he growt h rat e, and t he product of
t he int ercept and growt h rat e gives t he nucleat ion rat e.
Fig. 12. Plot of populat ion densit y as a f unct ion of size f or K N O
3
. = 15 min. For t he line, n = 16:528

exp ( 0:0090426L ); R = 0:99752;
slope = 1=G; int ercept = n
0
= B
0
=G.
Many indust rial cryst allizers operat e in a well-mixed or nearly well-mixed manner, and t he equat ions derived above can be used t o
describe t heir perf ormance. Furt hermore, t he simplicit y of t he equat ions describing an MSMPR cryst al lizer make experiment al equipment
conf igured t o meet t he assumpt ions leading t o equat ion 44 usef ul in det ermining nucleat ion and growt h kinet ics in syst ems of int erest .
From a series of runs at dif f erent operat ing condit ions, a correlat ion of nucleat ion and growt h kinet ics wit h appropriat e process
variables can be obt ained; t he result ing correlat ion can t hen be used t o guide eit her cryst allizer scaleup or t he development of an operat ing
st rat egy f or an exist ing cryst allizer. The variables af f ect ing nucleat ion and growt h kinet ics include t emperat ure, supersat urat ion, magma
densit y, and ext ernal st imuli, such as agit at ion or circulat ion rat e of t he magma. Empirical power-l aw f unct ions are used most f requent ly in
correlat ing nucleat ion and growt h rat es, but t he choice of t he independent variables can be just if ied f rom a mechanist ic perspect ive. For
example, syst ems t hat are believed t o f ollow secondary nucleat ion mechanisms should include a variable such as magma densit y t hat ref lect s
t he charact er of cryst als in t he cryst allizer. The most commonly used power-law f unct ions are
B
0
= k
1
s
b
M
j
T
(49)
G = k
2
s
g
(50)
I t is of t en dif f icult t o measure supersat urat ion, especially in syst ems t hat have high growt h rat es. Even t hough t he supersat urat ion in
CRYSTALLIZATION Vol 7
Kirk-Othmer Encyclopedia of Chemical Technology (4th Edition) 18
such syst ems is so small t hat it can be neglect ed in writ ing a solut e mass balance, it is import ant in set t ing nucleat ion and growt h rat es. I n
such inst ances it is convenient t o subst it ut e growt h rat e f or supersat urat ion by combining equat ions 49 and 50 t o get
B
0
= k
n
G
i
M
j
T
(51)
The const ant k
n
may depend on process variables such as t emperat ure, rat e of agit at ion or circulat ion, presence of impurit ies, and
ot her variables. I f suf f icient dat a are available, such quant it ies may be separat ed f rom t he const ant by adding more t erms in a power-law
correlat ion. The t erm k
n
is specif ic t o t he operat ing equipment and generally is not t ransf errable f rom one equipment scale t o anot her. The
syst em-specif ic const ant s i and j are obt ainable f rom experiment al dat a and may be used in scaleup, alt hough j may vary considerably wit h
mixing condit ions. I llust rat ion of t he use of dat a f rom a commercial cryst allizer t o obt ain t he kinet ic paramet ers k
n
, i , and j is available (61).
M ass Balance Constraints. From t he schemat ic diagram of a cont inuous cryst allizer shown in Figure 11, t he f ollowing mass
balance on solut e can be const ruct ed:
Q
i
c
i
= Q
0
c
0
+ Q
0
M
T
(52)
c
0
is det ermined by syst em kinet ics and const rained by a solidliquid equilibrium (solubilit y) relat ionship, which gives t he equilibrium
concent rat ion c* at t he syst em condit ions. The syst em (solut esolvent and cryst allizer) is charact erized by t he magnit ude of t he
supersat urat ion (c
0
c

) remaining in t he solut ion exit ing t he cryst allizer. I f t he mass balance is closed by subst it ut ing c* f or c
0
in equat ion
52, t he syst em is said t o be a f ast -growt h or class I I syst em. I f t he mass balance is not closed, signif icant supersat urat ion remains in t he
solut ion and t he syst em is said t o be a slow-growt h or class I syst em. I n ot her words, f or class I (slow-growt h) syst ems: c
0
> c

and
M
T
=
Q
i
Q
0
c
i
c
0
(53)
Values of process variables such as residence t ime may change t he syst em kinet ics t hat change c
0
and, in t urn, M
T
.
For class I I (f ast -growt h) syst ems: c
0
= c

and
M
T
=
Q
i
Q
0
c
i
c

(54)
Process variables do not change c* and, t heref ore, M
T
is const ant over modest ranges of operat ing condit ions.
CSD Characteristics for M SM PR Crystallizers. The perf ect ly mixed cryst allizer described in t he preceding discussion is
highly const rained and t he f orm of cryst al size dist ribut ions produced by such syst ems is f ixed. Such dist ribut ions have t he f ollowing
charact erist ics.
(1) Moment s of t he dist ribut ion can be calculat ed f or MSMPR cryst allizers by t he simple expression
m
j
= j !n
0
(G)
j + 1
(55)
Propert ies of t he dist ribut ion such as t ot al number of cryst als per unit volume, t ot al lengt h of cryst als per unit volume, t ot al area of cryst als
per unit volume, and t ot al volume of solids (cryst als) per unit volume may be explicit ly evaluat ed f rom t he moment equat ions.
(2) The dominant cryst al size L
D
is given by L
D
= 3G. This quant it y is also t he rat io m
3
/ m
2
, which is of t en given t he symbol L
3,2
.
(3) From t he def init ion of t he coef f icient of variat ion given by equat ion 41, cv = 50% f or an MSMPR cryst allizer. Such a cv may be
t oo large f or cert ain commercial product s, which means eit her t he cryst allizer must be alt ered or t he product must be screened t o separat e
t he desired f ract ion.
(4) The magma densit y M
T
(mass of cryst als per unit volume of slurry or liquor) may be obt ained f rom t he t hird moment of t he
populat ion densit y f unct ion and is given by
M
T
= 6k
v
n
0
(G)
4
(56)
Alt hough magma densit y is a f unct ion of t he kinet ic paramet ers n
0
and G , it of t en can be measured independent ly. I n such cases, it should
be used as a const raint in evaluat ing nucleat ion and growt h rat es f rom measured cryst al size dist ribut ions (62), especially if t he syst em of
int erest exhibit s t he charact erist ics of anomalous cryst al growt h.
(5) A pair of kinet ic paramet ers, one f or nucleat ion rat e and anot her f or growt h rat e, describe t he cr yst al size dist ribut ion f or a given
such syst ems is so small t hat it can be neglect ed in writ ing a solut e mass balance, it is import ant in set t ing nucleat ion and growt h rat es. I n
such inst ances it is convenient t o subst it ut e growt h rat e f or supersat urat ion by combining equat ions 49 and 50 t o get
B
0
= k
n
G
i
M
j
T
(51)
The const ant k
n
may depend on process variables such as t emperat ure, rat e of agit at ion or circulat ion, presence of impurit ies, and
ot her variables. I f suf f icient dat a are available, such quant it ies may be separat ed f rom t he const ant by adding more t erms in a power-law
correlat ion. The t erm k
n
is specif ic t o t he operat ing equipment and generally is not t ransf errable f rom one equipment scale t o anot her. The
syst em-specif ic const ant s i and j are obt ainable f rom experiment al dat a and may be used in scaleup, alt hough j may vary considerably wit h
mixing condit ions. I llust rat ion of t he use of dat a f rom a commercial cryst allizer t o obt ain t he kinet ic paramet ers k
n
, i , and j is available (61).
M ass Balance Constraints. From t he schemat ic diagram of a cont inuous cryst allizer shown in Figure 11, t he f ollowing mass
balance on solut e can be const ruct ed:
Q
i
c
i
= Q
0
c
0
+ Q
0
M
T
(52)
c
0
is det ermined by syst em kinet ics and const rained by a solidliquid equilibrium (solubilit y) relat ionship, which gives t he equilibrium
concent rat ion c* at t he syst em condit ions. The syst em (solut esolvent and cryst allizer) is charact erized by t he magnit ude of t he
supersat urat ion (c
0
c

) remaining in t he solut ion exit ing t he cryst allizer. I f t he mass balance is closed by subst it ut ing c* f or c
0
in equat ion
52, t he syst em is said t o be a f ast -growt h or class I I syst em. I f t he mass balance is not closed, signif icant supersat urat ion remains in t he
solut ion and t he syst em is said t o be a slow-growt h or class I syst em. I n ot her words, f or class I (slow-growt h) syst ems: c
0
> c

and
M
T
=
Q
i
Q
0
c
i
c
0
(53)
Values of process variables such as residence t ime may change t he syst em kinet ics t hat change c
0
and, in t urn, M
T
.
For class I I (f ast -growt h) syst ems: c
0
= c

and
M
T
=
Q
i
Q
0
c
i
c

(54)
Process variables do not change c* and, t heref ore, M
T
is const ant over modest ranges of operat ing condit ions.
CSD Characteristics for M SM PR Crystallizers. The perf ect ly mixed cryst allizer described in t he preceding discussion is
highly const rained and t he f orm of cryst al size dist ribut ions produced by such syst ems is f ixed. Such dist ribut ions have t he f ollowing
charact erist ics.
(1) Moment s of t he dist ribut ion can be calculat ed f or MSMPR cryst allizers by t he simple expression
m
j
= j !n
0
(G)
j + 1
(55)
Propert ies of t he dist ribut ion such as t ot al number of cryst als per unit volume, t ot al lengt h of cryst als per unit volume, t ot al area of cryst als
per unit volume, and t ot al volume of solids (cryst als) per unit volume may be explicit ly evaluat ed f rom t he moment equat ions.
(2) The dominant cryst al size L
D
is given by L
D
= 3G. This quant it y is also t he rat io m
3
/ m
2
, which is of t en given t he symbol L
3,2
.
(3) From t he def init ion of t he coef f icient of variat ion given by equat ion 41, cv = 50% f or an MSMPR cryst allizer. Such a cv may be
t oo large f or cert ain commercial product s, which means eit her t he cryst allizer must be alt ered or t he product must be screened t o separat e
t he desired f ract ion.
(4) The magma densit y M
T
(mass of cryst als per unit volume of slurry or liquor) may be obt ained f rom t he t hird moment of t he
populat ion densit y f unct ion and is given by
M
T
= 6k
v
n
0
(G)
4
(56)
Alt hough magma densit y is a f unct ion of t he kinet ic paramet ers n
0
and G , it of t en can be measured independent ly. I n such cases, it should
be used as a const raint in evaluat ing nucleat ion and growt h rat es f rom measured cryst al size dist ribut ions (62), especially if t he syst em of
int erest exhibit s t he charact erist ics of anomalous cryst al growt h.
(5) A pair of kinet ic paramet ers, one f or nucleat ion rat e and anot her f or growt h rat e, describe t he cr yst al size dist ribut ion f or a given
CRYSTALLIZATION Vol 7
Kirk-Othmer Encyclopedia of Chemical Technology (4th Edition) 19
set of cryst allizer operat ing condit ions. Variat ion in one of t he kinet ic paramet ers wit hout changing t he ot her is not possible. Accordingly,
t he relat ionship bet ween t hese paramet ers det ermines t he abilit y t o alt er t he charact erist ic propert ies (such as dominant size) of t he
dist ribut ion obt ained f rom an MSMPR cryst allizer (7).
Preferential Removal of Crystals. Cryst al size dist ribut ions produced in a perf ect ly mixed cont inuous cryst allizer are highly
const rained; t he f orm of t he CSD in such syst ems is det ermined ent irely by t he residence t ime dist ri but ion of a perf ect ly mixed cryst allizer.
Great er f lexibilit y can be obt ained t hrough int roduct ion of select ive removal devices t hat alt er t he residence t ime dist ribut ion of mat erials
f lowing f rom t he cryst allizer. The f unct ions of classif ied removal are best described in t erms of idealized models of clear-liquor advance,
classif ied-f ines removal, and classif ied-product removal.
Cl ear-l i quor advance is simply t he removal of mot her liquor f rom t he cryst allizer wit hout simult aneous removal of cryst als. The primary
object ive of fi nes removal is pref erent ial wit hdrawal f rom t he cryst allizer of cryst als whose size is below some specif ied val ue. Such cryst als
may be redissolved and t he result ing solut ion ret urned t o t he cryst allizer. Cl assi fi ed-product removal is carried out t o remove pref erent ially
t hose cryst als whose size is larger t han some specif ied value.
The ef f ect s of each select ive removal f unct ion on CSD can be described in t erms of t he populat ion densit y f unct ion n. I t is
convenient t o def ine f low rat es in t erms of clear liquor, which requires t he populat ion's densit y f unct ion t o be def ined on a clear-liquor
basis. I n t he present discussion, only syst ems exhibit ing invariant cryst al growt h are considered.
Clear-liquor advance reduces t he quant it y of liquor t hat must be processed by solidliquid separat ion equipment (f or example, a f ilt er
or a cent rif uge). The reduct ion in liquor f low t hrough t he separat ion equipment may allow use of smaller equipment f or a f ixed product ion
rat e or increased product ion t hrough f ixed equipment .
The f unct ion of clear-liquor advance can be illust rat ed by considering a simple operat ion, shown in Figure 13, in which Q
i
, Q
CL
, and
Q
0
represent volumet ric f low rat es of clear-liquor f ed t o t he cryst allizer, in t he clear-liquor advance, and in t he out put slurry. I n such
syst ems t he populat ion densit y f unct ion is given by t he expression
n = n
0
exp

L
G
p

(57)
where
p
= V=Q
0
. I t is clear t hat increasing Q
CL
decreases Q
0
and t hereby increases t he residence t ime of t he cryst als in t he cryst allizer.
Fig. 13. Simplif ied schemat ic diagram of clear-liquor advance or double-draw of f (D D O).
Clearly, t he f orm of t he populat ion densit y f unct ion result ing f rom a clear-liquor advance syst em is ident ical t o t hat expect ed f rom
perf ect ly mixed syst ems in which t
crystal s
is ident ical t o t
l i quor
. Unless t he increase in magma densit y associat ed wit h clear-liquor advance
result s in signif icant increases in nucleat ion, some increase in t he dominant cryst al size can be expect ed. I t has been observed t hat t he
increase in L
D
may be great er t han predict ed f rom t heory. This is caused by t he st ream being removed as clear liquor cont aining varying
amount s of f ines, which means t he syst em charact erist ics are t hose of classif ied-f ines removal.
As an idealizat ion of t he classif ied-f ines removal operat ion, assume t hat t wo st reams are wit hdrawn f rom t he cryst allizer, one
corresponding t o t he product st ream and t he ot her a f ines removal st ream. Such an arrangement is shown schemat ically in Figure 14. The
f low rat e of t he clear solut ion in t he product st ream is designat ed Q
0
and t he f low rat e of t he clear solut ion in t he f ines removal st ream is set
set of cryst allizer operat ing condit ions. Variat ion in one of t he kinet ic paramet ers wit hout changing t he ot her is not possible. Accordingly,
t he relat ionship bet ween t hese paramet ers det ermines t he abilit y t o alt er t he charact erist ic propert ies (such as dominant size) of t he
dist ribut ion obt ained f rom an MSMPR cryst allizer (7).
Preferential Removal of Crystals. Cryst al size dist ribut ions produced in a perf ect ly mixed cont inuous cryst allizer are highly
const rained; t he f orm of t he CSD in such syst ems is det ermined ent irely by t he residence t ime dist ri but ion of a perf ect ly mixed cryst allizer.
Great er f lexibilit y can be obt ained t hrough int roduct ion of select ive removal devices t hat alt er t he residence t ime dist ribut ion of mat erials
f lowing f rom t he cryst allizer. The f unct ions of classif ied removal are best described in t erms of idealized models of clear-liquor advance,
classif ied-f ines removal, and classif ied-product removal.
Cl ear-l i quor advance is simply t he removal of mot her liquor f rom t he cryst allizer wit hout simult aneous removal of cryst als. The primary
object ive of fi nes removal is pref erent ial wit hdrawal f rom t he cryst allizer of cryst als whose size is below some specif ied val ue. Such cryst als
may be redissolved and t he result ing solut ion ret urned t o t he cryst allizer. Cl assi fi ed-product removal is carried out t o remove pref erent ially
t hose cryst als whose size is larger t han some specif ied value.
The ef f ect s of each select ive removal f unct ion on CSD can be described in t erms of t he populat ion densit y f unct ion n. I t is
convenient t o def ine f low rat es in t erms of clear liquor, which requires t he populat ion's densit y f unct ion t o be def ined on a clear-liquor
basis. I n t he present discussion, only syst ems exhibit ing invariant cryst al growt h are considered.
Clear-liquor advance reduces t he quant it y of liquor t hat must be processed by solidliquid separat ion equipment (f or example, a f ilt er
or a cent rif uge). The reduct ion in liquor f low t hrough t he separat ion equipment may allow use of smaller equipment f or a f ixed product ion
rat e or increased product ion t hrough f ixed equipment .
The f unct ion of clear-liquor advance can be illust rat ed by considering a simple operat ion, shown in Figure 13, in which Q
i
, Q
CL
, and
Q
0
represent volumet ric f low rat es of clear-liquor f ed t o t he cryst allizer, in t he clear-liquor advance, and in t he out put slurry. I n such
syst ems t he populat ion densit y f unct ion is given by t he expression
n = n
0
exp

L
G
p

(57)
where
p
= V=Q
0
. I t is clear t hat increasing Q
CL
decreases Q
0
and t hereby increases t he residence t ime of t he cryst als in t he cryst allizer.
Fig. 13. Simplif ied schemat ic diagram of clear-liquor advance or double-draw of f (D D O).
Clearly, t he f orm of t he populat ion densit y f unct ion result ing f rom a clear-liquor advance syst em is ident ical t o t hat expect ed f rom
perf ect ly mixed syst ems in which t
crystal s
is ident ical t o t
l i quor
. Unless t he increase in magma densit y associat ed wit h clear-liquor advance
result s in signif icant increases in nucleat ion, some increase in t he dominant cryst al size can be expect ed. I t has been observed t hat t he
increase in L
D
may be great er t han predict ed f rom t heory. This is caused by t he st ream being removed as clear liquor cont aining varying
amount s of f ines, which means t he syst em charact erist ics are t hose of classif ied-f ines removal.
As an idealizat ion of t he classif ied-f ines removal operat ion, assume t hat t wo st reams are wit hdrawn f rom t he cryst allizer, one
corresponding t o t he product st ream and t he ot her a f ines removal st ream. Such an arrangement is shown schemat ically in Figure 14. The
f low rat e of t he clear solut ion in t he product st ream is designat ed Q
0
and t he f low rat e of t he clear solut ion in t he f ines removal st ream is set
CRYSTALLIZATION Vol 7
Kirk-Othmer Encyclopedia of Chemical Technology (4th Edition) 20
as (R 1)Q
0
. Furt hermore, assume t hat t he device used t o separat e f ines f rom larger cryst als f unct ions so t hat only cryst als below an
arbit rary size L
F
are in t he f ines removal st ream and t hat all cryst als below size L
F
have an equal probabilit y of being removed in t he f ines
removal st ream. Under t hese condit ions, t he cryst al size dist ribut ion is charact erized by t wo mean r esidence t imes, one f or t he f ines and t he
ot her f or cryst als larger t han L
F
. These quant it ies are relat ed by t he equat ions

F
=
V
RQ
0
=

R
(L < L
F
)
(58)
=
V
Q
0
(L L
F
)
(59)
where V is t he volume of clear solut ion in t he cryst allizer. Recognize t hat t he rat io of t he probabilit y of a cryst al smaller t han L
F
being
removed f rom t he cryst allizer t o t hat of cryst als larger t han L
F
being removed is R = =
F
.
Fig. 14. Simplif ied schemat ic diagram of classif ied-f ines removal.
For syst ems f ollowing invariant growt h t he cryst al populat ion densit y in each size range decays exponent ially wit h t he inverse of t he
product of growt h rat e and residence t ime. For a cont inuous dist ribut ion, t he populat ion densit ies of t he classif ied f ines and t he product
cryst als must be t he same at size L
F
. Accordingly, t he populat ion densit y f or a cryst allizer operat ing wit h classif ied-f ines removal is given by
n = n

exp

RL
G

(L L
F
)
(60)
n = n

exp

(R 1) L
F
G

exp

L
G

(L > L
F
)
(61)
Figure 15 shows how t he populat ion densit y f unct ion changes wit h t he addit ion of classif ied-f ines removal. I t is apparent f rom t he f igure
t hat f ines removal increases t he dominant cryst al size, but it also increases t he spread of t he dist ribut ion.
as (R 1)Q
0
. Furt hermore, assume t hat t he device used t o separat e f ines f rom larger cryst als f unct ions so t hat only cryst als below an
arbit rary size L
F
are in t he f ines removal st ream and t hat all cryst als below size L
F
have an equal probabilit y of being removed in t he f ines
removal st ream. Under t hese condit ions, t he cryst al size dist ribut ion is charact erized by t wo mean r esidence t imes, one f or t he f ines and t he
ot her f or cryst als larger t han L
F
. These quant it ies are relat ed by t he equat ions

F
=
V
RQ
0
=

R
(L < L
F
)
(58)
=
V
Q
0
(L L
F
)
(59)
where V is t he volume of clear solut ion in t he cryst allizer. Recognize t hat t he rat io of t he probabilit y of a cryst al smaller t han L
F
being
removed f rom t he cryst allizer t o t hat of cryst als larger t han L
F
being removed is R = =
F
.
Fig. 14. Simplif ied schemat ic diagram of classif ied-f ines removal.
For syst ems f ollowing invariant growt h t he cryst al populat ion densit y in each size range decays exponent ially wit h t he inverse of t he
product of growt h rat e and residence t ime. For a cont inuous dist ribut ion, t he populat ion densit ies of t he classif ied f ines and t he product
cryst als must be t he same at size L
F
. Accordingly, t he populat ion densit y f or a cryst allizer operat ing wit h classif ied-f ines removal is given by
n = n

exp

RL
G

(L L
F
)
(60)
n = n

exp

(R 1) L
F
G

exp

L
G

(L > L
F
)
(61)
Figure 15 shows how t he populat ion densit y f unct ion changes wit h t he addit ion of classif ied-f ines removal. I t is apparent f rom t he f igure
t hat f ines removal increases t he dominant cryst al size, but it also increases t he spread of t he dist ribut ion.
CRYSTALLIZATION Vol 7
Kirk-Othmer Encyclopedia of Chemical Technology (4th Edition) 21
Fig. 15. Populat ion densit y f unct ion f or product f rom cryst allizer wit h classif ied-f ines removal. Cut size L
F
= 150 m; R = 3:7.
A simple met hod f or implement at ion of classif ied-f ines removal is t o remove slurry f rom a set t ling zone in t he cryst allizer. The
set t ling zone can be creat ed by const ruct ing a baf f le t hat separat es t he zone f rom t he well-mixed port ion of t he vessel, as is t he case f or a
draf t -t ube-baf f le cryst allizer, or in small-scale syst ems, by simply insert ing a lengt h of pipe int o t he cryst allizer chamber. The separat ion of
cryst als in t he set t ling zone is based on t he dependence of set t ling velocit y on cryst al size; only t hose cryst als having a set t ling velocit y
great er t han t he upward velocit y of t he slurry remain in t he cryst allizer. As t he cross-sect ional ar ea of a set t ling zone is invariant , t he f low
rat e of slurry t hrough t he zone det ermines t he cut size L
F
, and it also det ermines t he paramet er R used in equat ions 5962.
Classif ied removal of course mat erial also can be used, as shown in Figure 16. I n a cryst allizer equipped wit h idealized
classif ied-product removal, cryst als above some size L
C
are removed at a rat e Z t imes t he removal rat e expect ed f or a perf ect ly mixed
cryst allizer, and cryst als smaller t han L
C
are not removed at all. L arger cryst als can be removed select ively t hrough t he use of an elut riat ion
leg, hydrocyclones, or screens. Using t he analysis of classif ied-f ines removal syst ems as a guide, i t can be shown t hat t he cryst al populat ion
densit y wit hin t he cryst allizer magma is given by t he equat ions
n = n
0
exp

L
G

(L L
C
)
(62)
n = n
0
exp

(Z 1) L
C
G

exp

ZL
G

(L > L
C
)
(63)
where t is def ined as t he residence t ime V / Q
0
. Figure 17 shows t he ef f ect s of classif ied-product removal on cryst al size dist ribut ion. The
charact erist ics of t he cryst al size dist ribut ion obt ained f rom a syst em wit h classif ied product removal show a narrower dist ribut ion (reduced
coef f icient of variat ion) and smaller dominant size. A more complet e discussion of t he implicat ions of classif ied-product removal, wit h
part icular at t ent ion given t o t he dist inct ion bet ween t he cryst al populat ion densit ies wit hin t he cr yst allizer and in t he product has been given
(7).
Fig. 15. Populat ion densit y f unct ion f or product f rom cryst allizer wit h classif ied-f ines removal. Cut size L
F
= 150 m; R = 3:7.
A simple met hod f or implement at ion of classif ied-f ines removal is t o remove slurry f rom a set t ling zone in t he cryst allizer. The
set t ling zone can be creat ed by const ruct ing a baf f le t hat separat es t he zone f rom t he well-mixed port ion of t he vessel, as is t he case f or a
draf t -t ube-baf f le cryst allizer, or in small-scale syst ems, by simply insert ing a lengt h of pipe int o t he cryst allizer chamber. The separat ion of
cryst als in t he set t ling zone is based on t he dependence of set t ling velocit y on cryst al size; only t hose cryst als having a set t ling velocit y
great er t han t he upward velocit y of t he slurry remain in t he cryst allizer. As t he cross-sect ional ar ea of a set t ling zone is invariant , t he f low
rat e of slurry t hrough t he zone det ermines t he cut size L
F
, and it also det ermines t he paramet er R used in equat ions 5962.
Classif ied removal of course mat erial also can be used, as shown in Figure 16. I n a cryst allizer equipped wit h idealized
classif ied-product removal, cryst als above some size L
C
are removed at a rat e Z t imes t he removal rat e expect ed f or a perf ect ly mixed
cryst allizer, and cryst als smaller t han L
C
are not removed at all. L arger cryst als can be removed select ively t hrough t he use of an elut riat ion
leg, hydrocyclones, or screens. Using t he analysis of classif ied-f ines removal syst ems as a guide, i t can be shown t hat t he cryst al populat ion
densit y wit hin t he cryst allizer magma is given by t he equat ions
n = n
0
exp

L
G

(L L
C
)
(62)
n = n
0
exp

(Z 1) L
C
G

exp

ZL
G

(L > L
C
)
(63)
where t is def ined as t he residence t ime V / Q
0
. Figure 17 shows t he ef f ect s of classif ied-product removal on cryst al size dist ribut ion. The
charact erist ics of t he cryst al size dist ribut ion obt ained f rom a syst em wit h classif ied product removal show a narrower dist ribut ion (reduced
coef f icient of variat ion) and smaller dominant size. A more complet e discussion of t he implicat ions of classif ied-product removal, wit h
part icular at t ent ion given t o t he dist inct ion bet ween t he cryst al populat ion densit ies wit hin t he cr yst allizer and in t he product has been given
(7).
CRYSTALLIZATION Vol 7
Kirk-Othmer Encyclopedia of Chemical Technology (4th Edition) 22
Fig. 16. Classif ied wit hdrawal of course cryst als.
Fig. 17. Ef f ect of classif ied-product removal on populat ion densit ies wit hin a cryst allizer and in t he cryst allizer product .
I t is possible t o obt ain bot h a narrowing of t he dist ribut ion and an increase in dominant size by combining pref erent ial removal of
f ines and course cryst als. I ncluding t he idealized removal f unct ions f or f ines and course cryst als i n a populat ion balance and assuming
invariant cryst al growt h will result in a populat ion densit y f unct ion wit hin t he cryst allizer given by equat ions 6466, Figure 18 illust rat es t he
ef f ect s of bot h removal f unct ions on populat ion densit y. This plot of populat ion densit y result s f rom sampling t he magma wit hin a
cryst allizer, not f rom sampling t he product st ream.
n = n
0
exp

RL
G

for L L
F
(64)
n = n
0
exp

(R 1) L
F
G

exp

L
G

for L
F
< L < L
C
(65)
Fig. 16. Classif ied wit hdrawal of course cryst als.
Fig. 17. Ef f ect of classif ied-product removal on populat ion densit ies wit hin a cryst allizer and in t he cryst allizer product .
I t is possible t o obt ain bot h a narrowing of t he dist ribut ion and an increase in dominant size by combining pref erent ial removal of
f ines and course cryst als. I ncluding t he idealized removal f unct ions f or f ines and course cryst als i n a populat ion balance and assuming
invariant cryst al growt h will result in a populat ion densit y f unct ion wit hin t he cryst allizer given by equat ions 6466, Figure 18 illust rat es t he
ef f ect s of bot h removal f unct ions on populat ion densit y. This plot of populat ion densit y result s f rom sampling t he magma wit hin a
cryst allizer, not f rom sampling t he product st ream.
n = n
0
exp

RL
G

for L L
F
(64)
n = n
0
exp

(R 1) L
F
G

exp

L
G

for L
F
< L < L
C
(65)
CRYSTALLIZATION Vol 7
Kirk-Othmer Encyclopedia of Chemical Technology (4th Edition) 23
n = n
0
exp

(R 1) L
F
G

exp

(Z 1) L
C
G

exp

ZL
G

for L L
C
(66)
Fig. 18. Populat ion densit y f unct ions of cryst als wit hin a cryst allizer, having bot h classif ied-f ines and classif ied-product removal and of
cryst als in t he product f rom such a cryst allizer.
The model of t he cryst allizer and select ive removal devices t hat led t o equat ions 6466 is ref erred t o as t he R-Z cryst allizer. I t is an
obvious idealizat ion of act ual cryst allizers because of t he perf ect cut s assumed at L
F
and L
C
. However, it is a usef ul approximat ion t o many
syst ems and it allows qualit at ive analyses of complex operat ions. The R-Z model may also be represent at ive of inadvert ant classif icat ion, ie,
f ines or course cryst als may be pref erent ially removed f rom a cryst allizer wit hout inst allat ion of specif ic hardware t o accomplish such an
object ive.
Alt hough many commercial cryst allizers operat e wit h some f orm of select ive cryst al removal, such devices can be dif f icult t o operat e
because of f ouling of heat exchanger surf aces or blinding of screens. I n addit ion, several invest igat ions ident if y int eract ions bet ween
classif ied f ines and course product removal as causes of cycling of a cryst al size dist ribut ion (7). Of t en such behavior can be minimized or
even eliminat ed by increasing t he f ines removal rat e (63,64).
Batch Crystallization. Cryst al size dist ribut ions obt ained f rom bat ch cryst allizers are af f ect ed by t he mode used t o generat e
supersat urat ion and t he rat e at which supersat urat ion is generat ed. For example, in a cooling mode t here are several avenues t hat can be
f ollowed in reducing t he t emperat ure of t he bat ch syst em, and t he same can be said f or t he generat ion of supersat urat ion by evaporat ion or
by addit ion of a nonsolvent or precipit ant . The complexit y of a bat ch operat ion can be illust rat ed by considering t he summaries of seeded
and unseeded operat ions shown in Figure 19.
n = n
0
exp

(R 1) L
F
G

exp

(Z 1) L
C
G

exp

ZL
G

for L L
C
(66)
Fig. 18. Populat ion densit y f unct ions of cryst als wit hin a cryst allizer, having bot h classif ied-f ines and classif ied-product removal and of
cryst als in t he product f rom such a cryst allizer.
The model of t he cryst allizer and select ive removal devices t hat led t o equat ions 6466 is ref erred t o as t he R-Z cryst allizer. I t is an
obvious idealizat ion of act ual cryst allizers because of t he perf ect cut s assumed at L
F
and L
C
. However, it is a usef ul approximat ion t o many
syst ems and it allows qualit at ive analyses of complex operat ions. The R-Z model may also be represent at ive of inadvert ant classif icat ion, ie,
f ines or course cryst als may be pref erent ially removed f rom a cryst allizer wit hout inst allat ion of specif ic hardware t o accomplish such an
object ive.
Alt hough many commercial cryst allizers operat e wit h some f orm of select ive cryst al removal, such devices can be dif f icult t o operat e
because of f ouling of heat exchanger surf aces or blinding of screens. I n addit ion, several invest igat ions ident if y int eract ions bet ween
classif ied f ines and course product removal as causes of cycling of a cryst al size dist ribut ion (7). Of t en such behavior can be minimized or
even eliminat ed by increasing t he f ines removal rat e (63,64).
Batch Crystallization. Cryst al size dist ribut ions obt ained f rom bat ch cryst allizers are af f ect ed by t he mode used t o generat e
supersat urat ion and t he rat e at which supersat urat ion is generat ed. For example, in a cooling mode t here are several avenues t hat can be
f ollowed in reducing t he t emperat ure of t he bat ch syst em, and t he same can be said f or t he generat ion of supersat urat ion by evaporat ion or
by addit ion of a nonsolvent or precipit ant . The complexit y of a bat ch operat ion can be illust rat ed by considering t he summaries of seeded
and unseeded operat ions shown in Figure 19.
CRYSTALLIZATION Vol 7
Kirk-Othmer Encyclopedia of Chemical Technology (4th Edition) 24
Fig. 19. Bat ch cryst allizer operat ion.
The cryst al size dist ribut ions result ing f rom t he operat ing st rat egies out lined in Figure 19 depend great ly on t he use of seeding, t he
rat e at which supersat urat ion is generat ed, and t hose variables t hat are import ant in t he prevailing mechanism of nucleat ion. Figures 20 and
21 summarize t he qualit at ive variat ions in CSD t hat may be observed in bat ch cryst allizat ion and t he r ole of adding seed cryst als t o such
syst ems.
Fig. 20. CSD charact erist ics f rom bat ch cryst allizat ion wit hout seeding.
Fig. 19. Bat ch cryst allizer operat ion.
The cryst al size dist ribut ions result ing f rom t he operat ing st rat egies out lined in Figure 19 depend great ly on t he use of seeding, t he
rat e at which supersat urat ion is generat ed, and t hose variables t hat are import ant in t he prevailing mechanism of nucleat ion. Figures 20 and
21 summarize t he qualit at ive variat ions in CSD t hat may be observed in bat ch cryst allizat ion and t he r ole of adding seed cryst als t o such
syst ems.
Fig. 20. CSD charact erist ics f rom bat ch cryst allizat ion wit hout seeding.
CRYSTALLIZATION Vol 7
Kirk-Othmer Encyclopedia of Chemical Technology (4th Edition) 25
Fig. 21. CSD charact erist ics f rom bat ch cryst allizat ion wit h seeding.
More quant it at ive relat ionships of t he CSD obt ained f rom bat ch operat ions can be developed t hrough f ormulat ion of a populat ion
balance. Using a populat ion densit y def ined in t erms of t he t ot al cryst allizer volume rat her t han on a specif ic basis (n = nV), t he general
populat ion balance given by equat ion 42 can be modif ied in recognit ion of t here being no f eed or product st reams:
@(nV)
@t
+
@(GnV)
@L
=
@ n
@t
+
@(G n)
@L
= 0
(67)
The solut ion t o t his equat ion requires an init ial condit ion (n at t = 0) and a boundary condit ion (n at a specif ic value of L ). Assuming
t hat cryst als are f ormed at zero size gives t he boundary condit ion:
n(0; t ) = n
0
(t ) =

B
0
(t )
G(0; t )
(68)
I dent if icat ion of an init ial condit ion is dif f icult because of t he problem of specif ying t he size di st ribut ion at t he inst ant nucleat ion occurs.
The dif f icult y is mit igat ed t hrough t he use of seeding, which would mean t hat t he init ial populat ion densit y f unct ion would correspond t o
t hat of t he seed cryst als:
n(L; 0) = n
S
(L)
(69)
where n
S
is t he populat ion densit y f unct ion of t he seed cryst als.
Moment s of t he populat ion densit y f unct ion, which are given by
m
j
=
Z
1
0
L
j
ndL
(70)
are especially usef ul in modeling cryst al size dist ribut ions in bat ch operat ions and in t he development of equat ions relat ing a cont rol variable
t o t ime. Recognizing t hat t he zero moment is t he t ot al number of cryst als in t he syst em it can be shown t hat
d m
0
dt
= n
0
G =

B
0
=
d

N
T
dt
(71)
From t he relat ionships of moment s t o propert ies of t he dist ribut ion, t he f ollowing equat ions can be derived:
d m
1
dt
= G m
0
)
d

L
T
dt
=

N
T
G
(72)
d m
2
dt
= 2G m
1
)
d

A
T
dt
= 2k
a

L
T
G
(73)
d m
3
dt
= 3G m
2
)
d

M
T
dt
= 3

k
v
k
a

A
T
G
(74)
where N
T
is t ot al number of cryst als, L
T
is t ot al cryst al lengt h, A
T
is t ot al surf ace area of t he cryst als, and M
T
is t ot al mass of cryst als in t he
cryst allizer. A solut e balance must also be sat isf ied:
d( V
C
)
dt
+
d

M
T
dt
= 0
(75)
where V is t he syst em volume, and c is solut e concent rat ion in t he solut ion.
Cont rol of supersat urat ion is an import ant f act or in obt aining cryst al size dist ribut ions of desired charact erist ics, and it would be
Fig. 21. CSD charact erist ics f rom bat ch cryst allizat ion wit h seeding.
More quant it at ive relat ionships of t he CSD obt ained f rom bat ch operat ions can be developed t hrough f ormulat ion of a populat ion
balance. Using a populat ion densit y def ined in t erms of t he t ot al cryst allizer volume rat her t han on a specif ic basis (n = nV), t he general
populat ion balance given by equat ion 42 can be modif ied in recognit ion of t here being no f eed or product st reams:
@(nV)
@t
+
@(GnV)
@L
=
@ n
@t
+
@(G n)
@L
= 0
(67)
The solut ion t o t his equat ion requires an init ial condit ion (n at t = 0) and a boundary condit ion (n at a specif ic value of L ). Assuming
t hat cryst als are f ormed at zero size gives t he boundary condit ion:
n(0; t ) = n
0
(t ) =

B
0
(t )
G(0; t )
(68)
I dent if icat ion of an init ial condit ion is dif f icult because of t he problem of specif ying t he size di st ribut ion at t he inst ant nucleat ion occurs.
The dif f icult y is mit igat ed t hrough t he use of seeding, which would mean t hat t he init ial populat ion densit y f unct ion would correspond t o
t hat of t he seed cryst als:
n(L; 0) = n
S
(L)
(69)
where n
S
is t he populat ion densit y f unct ion of t he seed cryst als.
Moment s of t he populat ion densit y f unct ion, which are given by
m
j
=
Z
1
0
L
j
ndL
(70)
are especially usef ul in modeling cryst al size dist ribut ions in bat ch operat ions and in t he development of equat ions relat ing a cont rol variable
t o t ime. Recognizing t hat t he zero moment is t he t ot al number of cryst als in t he syst em it can be shown t hat
d m
0
dt
= n
0
G =

B
0
=
d

N
T
dt
(71)
From t he relat ionships of moment s t o propert ies of t he dist ribut ion, t he f ollowing equat ions can be derived:
d m
1
dt
= G m
0
)
d

L
T
dt
=

N
T
G
(72)
d m
2
dt
= 2G m
1
)
d

A
T
dt
= 2k
a

L
T
G
(73)
d m
3
dt
= 3G m
2
)
d

M
T
dt
= 3

k
v
k
a

A
T
G
(74)
where N
T
is t ot al number of cryst als, L
T
is t ot al cryst al lengt h, A
T
is t ot al surf ace area of t he cryst als, and M
T
is t ot al mass of cryst als in t he
cryst allizer. A solut e balance must also be sat isf ied:
d( V
C
)
dt
+
d

M
T
dt
= 0
(75)
where V is t he syst em volume, and c is solut e concent rat ion in t he solut ion.
Cont rol of supersat urat ion is an import ant f act or in obt aining cryst al size dist ribut ions of desired charact erist ics, and it would be
CRYSTALLIZATION Vol 7
Kirk-Othmer Encyclopedia of Chemical Technology (4th Edition) 26
usef ul t o have a model relat ing rat e of cooling or evaporat ion or addit ion of diluent required t o maint ain a specif ied supersat urat ion in t he
cryst allizer. Cont rast t his t o t he uncont rolled sit uat ion of nat ural cooling in which t he heat t ransf er rat e is given by
Q = UA(T T
c
)
(76)
where U is a heat -t ransf er coef f icient , A is t he area available f or heat t ransf er, T is t he t emperat ure of t he magma, and T
c
is t he t emperat ure
of t he cooling f luid. I f U and T
c
are const ant s, t he maximum heat t ransf er rat e and t he highest rat e at which supersat urat ion is generat ed are
at t he beginning of t he process when T is highest . These condit ions can lead t o excessive primary nucleat ion and t he f ormat ion of
incrust at ions on t he heat -t ransf er surf aces.
Bet t er product charact erist ics are obt ained t hrough cont rol of t he rat e at which supersat urat ion (cooling, evaporat ion, and addit ion of
a nonsolvent or precipit ant ) is generat ed. An object ive of t he operat ion may be t o maint ain t he supersat urat ion at some const ant prescribed
value, usually below t he met ast able limit associat ed wit h primary nucleat ion. For example, t he bat ch may be cooled slowly at t he beginning
of t he cycle and more rapidly at t he end.
Formulat ions of populat ion balances on bat ch cryst allizers have been illust rat ed, and a variet y of operat ing st rat egies have been
considered (65). The result s are of t en complex and present dif f icult cont rol schemes at best . For example, suppose a model is needed t o
guide t he operat ion of a bat ch seeded cryst allizer so t hat isot hermal solvent evaporat ion can be accomplished at a rat e t hat gives a const ant
cryst al growt h rat e and no nucleat ion. I t is shown t hat t he evaporat ion rat e required is a cubic f unct ion of t ime and t he corresponding rat e
of heat input t o t he cryst allizer must be cont rolled accordingly. I f cooling was t o be used rat her t han evaporat ion, a similar analysis would
show t hat t he dependence of cryst allizer t emperat ure on t ime is highly nonlinear. Alt hough t he devel opment of a st rat egy f or generat ing
supersat urat ion can be aided by such analyses, t he init ial condit ions in t he models derived are based on propert ies of seed cryst als added t o
t he cryst allizer.
The advant ages of select ive removal of f ines f rom a bat ch cryst allizer have been demonst rat ed (66,67). These experiment al programs
showed narrowing of cryst al size dist ribut ions and suggest signif icant reduct ions in t he f ract ion of a product t hat would consist of f ines or
undersize mat erial.
Crystallizers and Crystallization Operations
Cryst allizat ion equipment can vary in sophist icat ion f rom a simple st irred t ank t o a complicat ed mul t iphase column, and t he operat ion can
range f rom allowing a vat of liquor t o cool t hrough exchanging heat wit h t he surroundings t o t he complex cont rol required of bat ch cyclic
operat ions. I n principle, t he object ives of t hese syst ems are all t he same: t o produce a pure product at a high yield wit h an accept able cryst al
size dist ribut ion. However, t he charact erist ics of t he cryst allizing syst em and desired propert ies of t he product of t en dict at e t hat a specif ic
cryst allizer be used in a part icular operat ing mode.
Crystallization from Solution. Cryst allizat ion t echniques are relat ed t o t he met hods used t o induce a driving f orce f or solids
f ormat ion and t o t he medium f rom which cryst als are obt ained. Several approaches are def ined in t he f ollowing discussion.
Cool i ng crystal l i zers use a heat sink t o remove bot h sensible heat f rom t he f eed st ream and t he heat of cryst allizat ion r eleased as cryst als
are f ormed. The heat sink may be no more t han t he ambient surroundings of a bat ch cryst allizer, or i t may be cooling wat er or anot her
process st ream.
E vaporati ve crystal l i zers generat e supersat urat ion by removing solvent , t hereby increasing solut e concent rat ion. These cryst allizers may
be operat ed under vacuum, and, in such circumst ances, it is necessary t o have a vacuum pump or eject or as a part of t he unit . I f t he boiling
point elevat ion of t he syst em is low (t hat is, t he dif f erence bet ween t he boiling point of a solut ion in t he cryst allizer and t he condensat ion
t emperat ure of pure solvent at t he syst em pressure), mechanical recompression of t he vapor obt ained f rom solvent evaporat ion can be
used t o produce a heat source t o drive t he operat ion.
E vaporati ve-cool i ng crystal l i zers are f ed wit h a liquor t hat is at a t emperat ure above t hat in t he cryst allizer. As t he f eed is int roduced t o t he
cryst allizer, which is at reduced pressure, solvent f lashes, t hereby concent rat ing t he solut e in t he result ing solut ion and reducing t he
t emperat ure of t he magma. The mode of t his operat ion can be degenerat ed t o t hat of a simple cooling cryst allizer by ret urning condensed
solvent t o t he cryst allizer body.
Sal ti ng-out crystal l i zati on operat es t hrough t he addit ion of a nonsolvent t o t he magma in a cryst allizer. The select ion of t he nonsolvent
is based on t he ef f ect of t he solvent on solubilit y, cost , propert ies t hat af f ect handling, int eract ion wit h product requirement s, and ease of
recovery. The ef f ect of adding a nonsolvent can be quit e complex as it increases t he volume required f or a given residence t ime and may
produce a highly nonideal mixt ure of solvent , nonsolvent , and solut e f rom which t he solvent is dif f i cult t o separat e.
Reacti ve crystal l i zati on addresses t hose operat ions in which a react ion occurs t o produce a cryst allizing solut e. The concent rat ion of t he
solut e f ormed generally is great er t han t hat corresponding t o solubilit y. I n a subset of syst ems, t he solubilit y is nearly zero and,
concomit ant ly, t he supersat urat ion produced by react ion is large. These are of t en ref erred t o as preci pi tati on operat ions, and cryst al size
dist ribut ions f rom t hem cont ain a large f ract ion of f ine cryst als.
usef ul t o have a model relat ing rat e of cooling or evaporat ion or addit ion of diluent required t o maint ain a specif ied supersat urat ion in t he
cryst allizer. Cont rast t his t o t he uncont rolled sit uat ion of nat ural cooling in which t he heat t ransf er rat e is given by
Q = UA(T T
c
)
(76)
where U is a heat -t ransf er coef f icient , A is t he area available f or heat t ransf er, T is t he t emperat ure of t he magma, and T
c
is t he t emperat ure
of t he cooling f luid. I f U and T
c
are const ant s, t he maximum heat t ransf er rat e and t he highest rat e at which supersat urat ion is generat ed are
at t he beginning of t he process when T is highest . These condit ions can lead t o excessive primary nucleat ion and t he f ormat ion of
incrust at ions on t he heat -t ransf er surf aces.
Bet t er product charact erist ics are obt ained t hrough cont rol of t he rat e at which supersat urat ion (cooling, evaporat ion, and addit ion of
a nonsolvent or precipit ant ) is generat ed. An object ive of t he operat ion may be t o maint ain t he supersat urat ion at some const ant prescribed
value, usually below t he met ast able limit associat ed wit h primary nucleat ion. For example, t he bat ch may be cooled slowly at t he beginning
of t he cycle and more rapidly at t he end.
Formulat ions of populat ion balances on bat ch cryst allizers have been illust rat ed, and a variet y of operat ing st rat egies have been
considered (65). The result s are of t en complex and present dif f icult cont rol schemes at best . For example, suppose a model is needed t o
guide t he operat ion of a bat ch seeded cryst allizer so t hat isot hermal solvent evaporat ion can be accomplished at a rat e t hat gives a const ant
cryst al growt h rat e and no nucleat ion. I t is shown t hat t he evaporat ion rat e required is a cubic f unct ion of t ime and t he corresponding rat e
of heat input t o t he cryst allizer must be cont rolled accordingly. I f cooling was t o be used rat her t han evaporat ion, a similar analysis would
show t hat t he dependence of cryst allizer t emperat ure on t ime is highly nonlinear. Alt hough t he devel opment of a st rat egy f or generat ing
supersat urat ion can be aided by such analyses, t he init ial condit ions in t he models derived are based on propert ies of seed cryst als added t o
t he cryst allizer.
The advant ages of select ive removal of f ines f rom a bat ch cryst allizer have been demonst rat ed (66,67). These experiment al programs
showed narrowing of cryst al size dist ribut ions and suggest signif icant reduct ions in t he f ract ion of a product t hat would consist of f ines or
undersize mat erial.
Crystallizers and Crystallization Operations
Cryst allizat ion equipment can vary in sophist icat ion f rom a simple st irred t ank t o a complicat ed mul t iphase column, and t he operat ion can
range f rom allowing a vat of liquor t o cool t hrough exchanging heat wit h t he surroundings t o t he complex cont rol required of bat ch cyclic
operat ions. I n principle, t he object ives of t hese syst ems are all t he same: t o produce a pure product at a high yield wit h an accept able cryst al
size dist ribut ion. However, t he charact erist ics of t he cryst allizing syst em and desired propert ies of t he product of t en dict at e t hat a specif ic
cryst allizer be used in a part icular operat ing mode.
Crystallization from Solution. Cryst allizat ion t echniques are relat ed t o t he met hods used t o induce a driving f orce f or solids
f ormat ion and t o t he medium f rom which cryst als are obt ained. Several approaches are def ined in t he f ollowing discussion.
Cool i ng crystal l i zers use a heat sink t o remove bot h sensible heat f rom t he f eed st ream and t he heat of cryst allizat ion r eleased as cryst als
are f ormed. The heat sink may be no more t han t he ambient surroundings of a bat ch cryst allizer, or i t may be cooling wat er or anot her
process st ream.
E vaporati ve crystal l i zers generat e supersat urat ion by removing solvent , t hereby increasing solut e concent rat ion. These cryst allizers may
be operat ed under vacuum, and, in such circumst ances, it is necessary t o have a vacuum pump or eject or as a part of t he unit . I f t he boiling
point elevat ion of t he syst em is low (t hat is, t he dif f erence bet ween t he boiling point of a solut ion in t he cryst allizer and t he condensat ion
t emperat ure of pure solvent at t he syst em pressure), mechanical recompression of t he vapor obt ained f rom solvent evaporat ion can be
used t o produce a heat source t o drive t he operat ion.
E vaporati ve-cool i ng crystal l i zers are f ed wit h a liquor t hat is at a t emperat ure above t hat in t he cryst allizer. As t he f eed is int roduced t o t he
cryst allizer, which is at reduced pressure, solvent f lashes, t hereby concent rat ing t he solut e in t he result ing solut ion and reducing t he
t emperat ure of t he magma. The mode of t his operat ion can be degenerat ed t o t hat of a simple cooling cryst allizer by ret urning condensed
solvent t o t he cryst allizer body.
Sal ti ng-out crystal l i zati on operat es t hrough t he addit ion of a nonsolvent t o t he magma in a cryst allizer. The select ion of t he nonsolvent
is based on t he ef f ect of t he solvent on solubilit y, cost , propert ies t hat af f ect handling, int eract ion wit h product requirement s, and ease of
recovery. The ef f ect of adding a nonsolvent can be quit e complex as it increases t he volume required f or a given residence t ime and may
produce a highly nonideal mixt ure of solvent , nonsolvent , and solut e f rom which t he solvent is dif f i cult t o separat e.
Reacti ve crystal l i zati on addresses t hose operat ions in which a react ion occurs t o produce a cryst allizing solut e. The concent rat ion of t he
solut e f ormed generally is great er t han t hat corresponding t o solubilit y. I n a subset of syst ems, t he solubilit y is nearly zero and,
concomit ant ly, t he supersat urat ion produced by react ion is large. These are of t en ref erred t o as preci pi tati on operat ions, and cryst al size
dist ribut ions f rom t hem cont ain a large f ract ion of f ine cryst als.
CRYSTALLIZATION Vol 7
Kirk-Othmer Encyclopedia of Chemical Technology (4th Edition) 27
Supercri ti cal fl ui d sol vents are t hose f ormed by operat ing a syst em above t he crit ical condit ions of t he solvent . Solubilit ies of many
solut es in such f luids of t en is much great er t han t hose f ound f or t he same solut es but wit h t he f lui d at subat mospheric condit ions. Recent ly,
t here has been considerable int erest in using supercrit ical f luids as solvent s in t he product ion of cert ain cryst alline mat erials because of t he
special propert ies of t he product cryst als. Rapid expansion of a supercrit ical syst em rapidly reduces t he solubilit y of a solut e t hroughout t he
ent ire mixt ure. The result ing high supersat urat ion produces f ine cryst als of relat ively unif orm size. Moreover, t he solvent poses no
purif icat ion problems because it simply becomes a gas as t he syst em condit ions are reduced below cri t ical.
Crystallizers. The basic requirement s of a syst em involving cryst allizat ion f rom solut ion are as f ollows: (1) a means of generat ing
supersat urat ion in a f ashion commensurat e wit h t he requirement s of producing a sat isf act ory cryst al size dist ribut ion, (2) a vessel t o provide
suf f icient residence t ime f or cryst als t o grow t o a desired size, and (3) mixing t o provide a unif orm environment f or cryst al growt h. There
are numerous manuf act urers of cryst allizat ion equipment ; in addit ion, many chemical companies design t heir own cryst allizers based on
expert ise developed wit hin t heir organizat ions. Rat her t han at t empt t o describe t he variet y of speci al cryst allizers t hat can be f ound in t he
market place, t his sect ion provides a brief general survey of t ypes of cryst allizers t hat use t he modes out lined above. Great er det ail can be
f ound in t he lit erat ure (68,69).
The f orced-circulat ion cryst allizer is a simple unit designed t o provide high heat -t ransf er coef f icient s in eit her an evaporat ive or a
cooling mode. Figure 22 shows a schemat ic diagram of a f orced-circulat ion cryst allizer t hat wit hdraws a slurry f rom t he cryst allizer body
and pumps it t hrough a heat exchanger where heat may be eit her added t o or removed f rom t he slurry. Heat t ransf erred t o t he circulat ing
magma causes evaporat ion of solvent as t he magma is ret urned t o t he cryst allizer, whereas heat removal lowers t he t emperat ure of t he
circulat ing magma. Forced circulat ion is used t o cont rol circulat ion rat es and velocit ies past t he heat -t ransf er surf aces.
Fig. 22. Schemat ic diagram of f orced circulat ion cryst allizer.
When cooling is t he select ed mode by which supersat urat ion is generat ed, heat can be t ransf erred t hr ough an ext ernal cooling
surf ace, as shown in Figure 22, or t hrough coils or a jacket int ernal t o t he cryst allizer body. The higher heat -t ransf er coef f icient s t hat can be
achieved wit h f orced circulat ion allows t he t emperat ure dif f erence bet ween heat source and sink t o be minimal, t hereby reducing f ormat ion
of encrust at ions on t he heat t ransf er surf ace. The operat ion of cooling cryst allizers is limit ed by t he t endency of t he solut e t o f orm
encrust at ions on t he cooling surf ace, so t hat t he t emperat ure of t he cooling f luid and t he t emperat ure decrease of t he slurry f lowing
t hrough t he heat exchanger may be limit ed. I t is not uncommon t o limit t he decrease in magma t emperat ure t o about 3 t o 5C; t heref ore,
bot h t he circulat ion rat e and heat -t ransf er surf ace must be large.
The f eed in cooling cryst allizers should be rapidly mixed wit h t he magma so as t o minimize t he occur rence of regions of high
supersat urat ion, which lead t o excessive nucleat ion. Anot her f act or t hat can lead t o degradat ion of t he cryst al size dist ribut ion is t he t ype of
pump used in t he circulat ion loop; an inappropriat e pump can cause at t rit ion of t he cryst als t hrough abrasion, f ract ure, or shear, and most
commercial syst ems use specially designed axial-f low pumps t hat provide high f low rat es and low heads.
I f t he charact erist ics of t he syst em are such t hat t he operat ing t emperat ure of t he cryst allizer is low in comparison t o t he t emperat ure
of cooling wat er, or if t here are severe problems wit h t he f ormat ion of encrust at ions, direct -cont act ref rigerat ion can be used. A ref rigerant
is mixed wit h t he cryst allizer cont ent s and vaporized at t he magma surf ace. On vaporizing, t he ref ri gerant removes suf f icient heat f rom t he
magma t o cool t he f eed and remove t he heat of cryst allizat ion. The ref rigerant vapor must be compressed, condensed, and recycled f or t he
process t o be economical. Moreover, t he ref rigerant must be insoluble in t he liquor t o minimize losses and product cont aminat ion.
Scale f ormat ion on t he heat exchanger surf aces or at t he vapor liquid int erf ace in t he cryst allizer can cause operat ional problems
Supercri ti cal fl ui d sol vents are t hose f ormed by operat ing a syst em above t he crit ical condit ions of t he solvent . Solubilit ies of many
solut es in such f luids of t en is much great er t han t hose f ound f or t he same solut es but wit h t he f lui d at subat mospheric condit ions. Recent ly,
t here has been considerable int erest in using supercrit ical f luids as solvent s in t he product ion of cert ain cryst alline mat erials because of t he
special propert ies of t he product cryst als. Rapid expansion of a supercrit ical syst em rapidly reduces t he solubilit y of a solut e t hroughout t he
ent ire mixt ure. The result ing high supersat urat ion produces f ine cryst als of relat ively unif orm size. Moreover, t he solvent poses no
purif icat ion problems because it simply becomes a gas as t he syst em condit ions are reduced below cri t ical.
Crystallizers. The basic requirement s of a syst em involving cryst allizat ion f rom solut ion are as f ollows: (1) a means of generat ing
supersat urat ion in a f ashion commensurat e wit h t he requirement s of producing a sat isf act ory cryst al size dist ribut ion, (2) a vessel t o provide
suf f icient residence t ime f or cryst als t o grow t o a desired size, and (3) mixing t o provide a unif orm environment f or cryst al growt h. There
are numerous manuf act urers of cryst allizat ion equipment ; in addit ion, many chemical companies design t heir own cryst allizers based on
expert ise developed wit hin t heir organizat ions. Rat her t han at t empt t o describe t he variet y of speci al cryst allizers t hat can be f ound in t he
market place, t his sect ion provides a brief general survey of t ypes of cryst allizers t hat use t he modes out lined above. Great er det ail can be
f ound in t he lit erat ure (68,69).
The f orced-circulat ion cryst allizer is a simple unit designed t o provide high heat -t ransf er coef f icient s in eit her an evaporat ive or a
cooling mode. Figure 22 shows a schemat ic diagram of a f orced-circulat ion cryst allizer t hat wit hdraws a slurry f rom t he cryst allizer body
and pumps it t hrough a heat exchanger where heat may be eit her added t o or removed f rom t he slurry. Heat t ransf erred t o t he circulat ing
magma causes evaporat ion of solvent as t he magma is ret urned t o t he cryst allizer, whereas heat removal lowers t he t emperat ure of t he
circulat ing magma. Forced circulat ion is used t o cont rol circulat ion rat es and velocit ies past t he heat -t ransf er surf aces.
Fig. 22. Schemat ic diagram of f orced circulat ion cryst allizer.
When cooling is t he select ed mode by which supersat urat ion is generat ed, heat can be t ransf erred t hr ough an ext ernal cooling
surf ace, as shown in Figure 22, or t hrough coils or a jacket int ernal t o t he cryst allizer body. The higher heat -t ransf er coef f icient s t hat can be
achieved wit h f orced circulat ion allows t he t emperat ure dif f erence bet ween heat source and sink t o be minimal, t hereby reducing f ormat ion
of encrust at ions on t he heat t ransf er surf ace. The operat ion of cooling cryst allizers is limit ed by t he t endency of t he solut e t o f orm
encrust at ions on t he cooling surf ace, so t hat t he t emperat ure of t he cooling f luid and t he t emperat ure decrease of t he slurry f lowing
t hrough t he heat exchanger may be limit ed. I t is not uncommon t o limit t he decrease in magma t emperat ure t o about 3 t o 5C; t heref ore,
bot h t he circulat ion rat e and heat -t ransf er surf ace must be large.
The f eed in cooling cryst allizers should be rapidly mixed wit h t he magma so as t o minimize t he occur rence of regions of high
supersat urat ion, which lead t o excessive nucleat ion. Anot her f act or t hat can lead t o degradat ion of t he cryst al size dist ribut ion is t he t ype of
pump used in t he circulat ion loop; an inappropriat e pump can cause at t rit ion of t he cryst als t hrough abrasion, f ract ure, or shear, and most
commercial syst ems use specially designed axial-f low pumps t hat provide high f low rat es and low heads.
I f t he charact erist ics of t he syst em are such t hat t he operat ing t emperat ure of t he cryst allizer is low in comparison t o t he t emperat ure
of cooling wat er, or if t here are severe problems wit h t he f ormat ion of encrust at ions, direct -cont act ref rigerat ion can be used. A ref rigerant
is mixed wit h t he cryst allizer cont ent s and vaporized at t he magma surf ace. On vaporizing, t he ref ri gerant removes suf f icient heat f rom t he
magma t o cool t he f eed and remove t he heat of cryst allizat ion. The ref rigerant vapor must be compressed, condensed, and recycled f or t he
process t o be economical. Moreover, t he ref rigerant must be insoluble in t he liquor t o minimize losses and product cont aminat ion.
Scale f ormat ion on t he heat exchanger surf aces or at t he vapor liquid int erf ace in t he cryst allizer can cause operat ional problems
CRYSTALLIZATION Vol 7
Kirk-Othmer Encyclopedia of Chemical Technology (4th Edition) 28
wit h evaporat ive cryst allizers. Such problems can be overcome by not allowing vaporizat ion or excessive t emperat ures wit hin t he exchanger
and by proper int roduct ion of t he circulat ing magma int o t he cryst allizer. The lat t er may be accompl ished by int roducing t he magma below
t he surf ace of t he magma in t he cryst allizer, so t hat all vaporizat ion occurs f rom a well-mixed zone or by int roducing t he magma so as t o
induce a swirling mot ion t hat is int ended t o dislodge encrust at ions f rom t he wall of t he cryst allizer at t he vaporliquid int erf ace.
Special devices f or classif icat ion of cryst als may be used in some applicat ions. Figure 23 shows a draf t -t ube-baf f le (D TB) cryst allizer
designed t o provide pref erent ial removal of bot h f ines and classif ied product . Feed is int roduced t o t he f ines circulat ion line so t hat nuclei
result ing f rom f eed int roduct ion can be dissolved as t he st ream f lows t hrough t he f ines dissolut ion exchanger. A quiescent zone is f ormed
bet ween t he baf f le ext ending int o t he chamber and t he out side wall of t he cryst allizer. Flow t hrough t he quiescent zone can be adjust ed so
t hat cryst als below a cert ain size (det ermined by set t ling velocit y) are removed in t he f ines dissol ut ion circuit .
Fig. 23. Schemat ic diagram of draf t -t ube-baf f le cryst allizer.
Anot her t ype of cryst allizer is t he Oslo-t ype unit shown in Figure 24. I n unit s of t his t ype, t he object is t o f orm a supersat urat ed
solut ion in t he upper chamber and t hen relieve t he supersat urat ion t hrough growt h in t he lower chamber. The use of t he downf low pipe in
t he cryst allizer provides good mixing in t he growt h chamber.
wit h evaporat ive cryst allizers. Such problems can be overcome by not allowing vaporizat ion or excessive t emperat ures wit hin t he exchanger
and by proper int roduct ion of t he circulat ing magma int o t he cryst allizer. The lat t er may be accompl ished by int roducing t he magma below
t he surf ace of t he magma in t he cryst allizer, so t hat all vaporizat ion occurs f rom a well-mixed zone or by int roducing t he magma so as t o
induce a swirling mot ion t hat is int ended t o dislodge encrust at ions f rom t he wall of t he cryst allizer at t he vaporliquid int erf ace.
Special devices f or classif icat ion of cryst als may be used in some applicat ions. Figure 23 shows a draf t -t ube-baf f le (D TB) cryst allizer
designed t o provide pref erent ial removal of bot h f ines and classif ied product . Feed is int roduced t o t he f ines circulat ion line so t hat nuclei
result ing f rom f eed int roduct ion can be dissolved as t he st ream f lows t hrough t he f ines dissolut ion exchanger. A quiescent zone is f ormed
bet ween t he baf f le ext ending int o t he chamber and t he out side wall of t he cryst allizer. Flow t hrough t he quiescent zone can be adjust ed so
t hat cryst als below a cert ain size (det ermined by set t ling velocit y) are removed in t he f ines dissol ut ion circuit .
Fig. 23. Schemat ic diagram of draf t -t ube-baf f le cryst allizer.
Anot her t ype of cryst allizer is t he Oslo-t ype unit shown in Figure 24. I n unit s of t his t ype, t he object is t o f orm a supersat urat ed
solut ion in t he upper chamber and t hen relieve t he supersat urat ion t hrough growt h in t he lower chamber. The use of t he downf low pipe in
t he cryst allizer provides good mixing in t he growt h chamber.
CRYSTALLIZATION Vol 7
Kirk-Othmer Encyclopedia of Chemical Technology (4th Edition) 29
Fig. 24. Schemat ic diagram of an Oslo cryst allizer.
M elt Crystallization. The use of a solvent can be avoided in some syst ems. I n such cases, t he syst em operat es wit h heat as a
separat ing agent , as do several processes involving cryst allizat ion f rom solut ion, but f ormat ion of cryst alline mat erial is f rom a melt of t he
cryst allizing species rat her t han a solut ion.
For t he f ollowing reasons, melt cryst allizat ion holds great promise in sit uat ions in which it can be subst it ut ed f or cryst allizat ion f rom
solut ion: (1) Wit hout t he need t o recover and maint ain t he purit y of a solvent , processing cost s are reduced subst ant ially. (2) Because t here
is no cont aminat ed solvent t o handle, melt cryst allizat ion may be more environment ally benign. (3) Energy cost s f ound in evaporat ive
cryst allizat ion obviously would be reduced if it is possible t o produce a desired solid wit hout t he need t o evaporat e solvent . (4) Melt
cryst allizat ion may be a reasonable alt ernat ive t o ot her separat ion and purif icat ion processes, because t he heat of vaporizat ion of most
volat ile organic mat erials is bet ween t wo and f ive t imes t heir heat of f usion. An analysis of t he energy requirement s in melt processes
concludes t hat such processes can compet e wit h ot her t hermal separat ion t echniques only if t he plant is well designed and t he process
precisely cont rolled (70).
Melt cryst allizat ion is carried out eit her wit h a suspension of cryst als or an advancing f ront (layer) of solids, alt hough a more complet e
cat egorizat ion of melt cryst allizat ion is available (71). Following is a brief review of processes in which melt cryst allizat ion is used; a more
complet e review, including a worked out case st udy f or syst em design, is available (69).
A suspension of cryst als f ormed f rom t he melt may be cont act ed by well-mixed mot her liquor or t he cr yst als may be moved
count ercurrent ly t o liquor f low in a vert ical or horizont al column. I n column cryst allizers, cryst al s are moved in a specif ic direct ion by
gravit y or rot at ing blades. The cryst als are melt ed by t he addit ion of heat when t hey reach a designat ed end of t he cryst allizer; a port ion of
t he melt is removed as product and t he remainder is ret urned t o t he syst em t o f low count ercurrent ly t o and t o wash t he product cryst als.
One of t he early column cryst allizers was t hat int roduced f or t he separat ion of xylene isomers (see X YL EN E and ETH YL BEN Z EN E). I n
t his unit , shown schemat ically in Figure 25, p-xylene cryst als are f ormed in a scraped-surf ace chiller above t he column and f ed t o t he
column. The cryst als move downward count er-current ly t o impure liquid in t he upper port ion of t he column and melt ed p-xylene in t he
lower part of t he column. I mpure liquor is wit hdrawn f rom an appropriat e point near t he t op of t he column of cryst als while pure product ,
p-xylene, is removed f rom t he bot t om of t he column. The pulse unit drives melt up t he column as ref lux and int o a product receiver.
Fig. 24. Schemat ic diagram of an Oslo cryst allizer.
M elt Crystallization. The use of a solvent can be avoided in some syst ems. I n such cases, t he syst em operat es wit h heat as a
separat ing agent , as do several processes involving cryst allizat ion f rom solut ion, but f ormat ion of cryst alline mat erial is f rom a melt of t he
cryst allizing species rat her t han a solut ion.
For t he f ollowing reasons, melt cryst allizat ion holds great promise in sit uat ions in which it can be subst it ut ed f or cryst allizat ion f rom
solut ion: (1) Wit hout t he need t o recover and maint ain t he purit y of a solvent , processing cost s are reduced subst ant ially. (2) Because t here
is no cont aminat ed solvent t o handle, melt cryst allizat ion may be more environment ally benign. (3) Energy cost s f ound in evaporat ive
cryst allizat ion obviously would be reduced if it is possible t o produce a desired solid wit hout t he need t o evaporat e solvent . (4) Melt
cryst allizat ion may be a reasonable alt ernat ive t o ot her separat ion and purif icat ion processes, because t he heat of vaporizat ion of most
volat ile organic mat erials is bet ween t wo and f ive t imes t heir heat of f usion. An analysis of t he energy requirement s in melt processes
concludes t hat such processes can compet e wit h ot her t hermal separat ion t echniques only if t he plant is well designed and t he process
precisely cont rolled (70).
Melt cryst allizat ion is carried out eit her wit h a suspension of cryst als or an advancing f ront (layer) of solids, alt hough a more complet e
cat egorizat ion of melt cryst allizat ion is available (71). Following is a brief review of processes in which melt cryst allizat ion is used; a more
complet e review, including a worked out case st udy f or syst em design, is available (69).
A suspension of cryst als f ormed f rom t he melt may be cont act ed by well-mixed mot her liquor or t he cr yst als may be moved
count ercurrent ly t o liquor f low in a vert ical or horizont al column. I n column cryst allizers, cryst al s are moved in a specif ic direct ion by
gravit y or rot at ing blades. The cryst als are melt ed by t he addit ion of heat when t hey reach a designat ed end of t he cryst allizer; a port ion of
t he melt is removed as product and t he remainder is ret urned t o t he syst em t o f low count ercurrent ly t o and t o wash t he product cryst als.
One of t he early column cryst allizers was t hat int roduced f or t he separat ion of xylene isomers (see X YL EN E and ETH YL BEN Z EN E). I n
t his unit , shown schemat ically in Figure 25, p-xylene cryst als are f ormed in a scraped-surf ace chiller above t he column and f ed t o t he
column. The cryst als move downward count er-current ly t o impure liquid in t he upper port ion of t he column and melt ed p-xylene in t he
lower part of t he column. I mpure liquor is wit hdrawn f rom an appropriat e point near t he t op of t he column of cryst als while pure product ,
p-xylene, is removed f rom t he bot t om of t he column. The pulse unit drives melt up t he column as ref lux and int o a product receiver.
CRYSTALLIZATION Vol 7
Kirk-Othmer Encyclopedia of Chemical Technology (4th Edition) 30
Fig. 25. Schemat ic diagram of a syst em used t o separat e xylene isomers (69). PC = pressure cont rol, TC = t emperat ure cont rol, and
FC = ow cont rol.
A horizont al column is t ypif ied by t he Brodie Purif ier, which is shown schemat ically in Figure 26. Feed ent ers t he column bet ween
recovery and ref ining sect ions, and cryst als exit t he ref ining sect ion and pass t hrough a purif ying sect ion. The purif ying sect ion is a wash
column in which t he cryst als are cont act ed wit h melt generat ed at t he bot t om of t he column.
Fig. 26. Schemat ic diagram of Brodie Purif ier. L = liquid; C = cryst als (69).
Fig. 25. Schemat ic diagram of a syst em used t o separat e xylene isomers (69). PC = pressure cont rol, TC = t emperat ure cont rol, and
FC = ow cont rol.
A horizont al column is t ypif ied by t he Brodie Purif ier, which is shown schemat ically in Figure 26. Feed ent ers t he column bet ween
recovery and ref ining sect ions, and cryst als exit t he ref ining sect ion and pass t hrough a purif ying sect ion. The purif ying sect ion is a wash
column in which t he cryst als are cont act ed wit h melt generat ed at t he bot t om of t he column.
Fig. 26. Schemat ic diagram of Brodie Purif ier. L = liquid; C = cryst als (69).
CRYSTALLIZATION Vol 7
Kirk-Othmer Encyclopedia of Chemical Technology (4th Edition) 31
I n advancing-f ront or layer melt cryst allizat ions, mot her liquor f lows over a cooled surf ace on which mat erial is cryst allized. The
advancing f ront of cryst als grows in t he direct ion f rom t he cooled surf ace int o t he mot her liquor. A variet y of t echniques can be used t o
t ake advant age of t his t ype of operat ion.
Figure 27 is a schemat ic diagram of t he MWB process, which uses an operat ion in which t here are several st eps in a bat ch cycle.
Cryst al growt h is on t he inside of a bat t ery of t ubes t hrough which melt is f lowing, and t he melt may f low as a f alling f ilm or it can be
pumped t hrough t he t ubes. The process includes t he f ollowing st eps:
(1) Flow of mot her liquor t hrough t he cooled t ubes is init iat ed, and cryst als are grown on t he t ube surf aces. The heat t ransf er rat e should
be cont rolled so as t o moderat e cryst al growt h, t hereby producing a relat ively unif orm layer of high purit y solids.
(2) When suf f icient cryst al mass has been f ormed, melt f low is st opped and residual mot her liquor is drained f rom t he unit .
(3) The solid purit y is enhanced by applying heat and causing impurit ies t o f low f rom t he heat ed solids t hrough a process known as
sweat ing.
(4) Af t er sweat ing, eit her t he cycle is ret urned t o st ep 1 and addit ional solids are deposit ed or t he solids present on t he t ube wall are
melt ed and recovered as product .
(5) The recovered product melt can be put t hrough t he cycle again t o increase purit y, or f resh f eed can be int roduced t o t he cycle.
Fig. 27. Schemat ic diagram of t he MWB melt cryst allizat ion process.
BI BLI OGRAPH Y
" Cryst allizat ion," in E CT 1st ed., Vol. 4, pp. 619636, by A. Ralph Thompson, Universit y of Pennsylvania; in E CT 2nd ed., Vol. 6, pp.
482515, by J. W. Mullin, Universit y of L ondon; in E CT 3rd ed., Vol. 7, pp. 243285, by J. W. Mullin, Universit y of L ondon.
1. N at ional Research Council, F ronti ers i n Chemi cal E ngi neeri ng: Research N eeds and Opportuni ti es, N at ional Academy Press, Washingt on,
D .C., 1988, Chapt . 3.
2. R. M. Felder and R. W. Rousseau, E l ementary Pri nci pl es of Chemi cal Processes, 2nd ed., John Wiley & Sons I nc., N ew York, 1986.
3. R. H. Perry and D . W. Green, eds., Perry' s Chemi cal E ngi neers' H andbook , McGraw-Hill Book Co., I nc., N ew York, 1984, p. 399.
4. H. Charmolue and R. W. Rousseau, A I ChE J. 37, 1121 (1991).
5. J. W. Mullin, Crystal l i zati on, 2nd ed., CRC Press, Cleveland, Ohio, 1972.
6. H. A. Miers and F. I ssac, in H. E. Buckley, Crystal G rowth, John Wiley & Sons, I nc., N ew York, 1951, p. 7.
7. A. D . Randolph and M. A. L arson, T heory of Parti cul ate Processes, 2nd ed., Academic Press, I nc., N ew York, 1988.
8. J. Garside and Roger J. D avey, Chem. E ng. Commun. 4, 393 (1980).
9. M. A. L arson, A I ChE Symp. Ser., 80(240), 39 (1984).
10. M. W. Girolami and R. W. Rousseau, I nd. E ng. Chem. Process D es. D ev. 25, 66 (1986).
11. C. Y. Sung, J. Est rin, and G. R. Youngquist , A I ChE J. 19, 957 (1973).
12. R. E. A. Mason and R. F. St rickland-Const able, T rans. F araday Soc., 62(pt . 2), 455 (1966).
13. D . P. L al, R. E. A. Mason, and R. F. St rickland-Const able, J. Cryst. G rowth 5, 1 (1969).
I n advancing-f ront or layer melt cryst allizat ions, mot her liquor f lows over a cooled surf ace on which mat erial is cryst allized. The
advancing f ront of cryst als grows in t he direct ion f rom t he cooled surf ace int o t he mot her liquor. A variet y of t echniques can be used t o
t ake advant age of t his t ype of operat ion.
Figure 27 is a schemat ic diagram of t he MWB process, which uses an operat ion in which t here are several st eps in a bat ch cycle.
Cryst al growt h is on t he inside of a bat t ery of t ubes t hrough which melt is f lowing, and t he melt may f low as a f alling f ilm or it can be
pumped t hrough t he t ubes. The process includes t he f ollowing st eps:
(1) Flow of mot her liquor t hrough t he cooled t ubes is init iat ed, and cryst als are grown on t he t ube surf aces. The heat t ransf er rat e should
be cont rolled so as t o moderat e cryst al growt h, t hereby producing a relat ively unif orm layer of high purit y solids.
(2) When suf f icient cryst al mass has been f ormed, melt f low is st opped and residual mot her liquor is drained f rom t he unit .
(3) The solid purit y is enhanced by applying heat and causing impurit ies t o f low f rom t he heat ed solids t hrough a process known as
sweat ing.
(4) Af t er sweat ing, eit her t he cycle is ret urned t o st ep 1 and addit ional solids are deposit ed or t he solids present on t he t ube wall are
melt ed and recovered as product .
(5) The recovered product melt can be put t hrough t he cycle again t o increase purit y, or f resh f eed can be int roduced t o t he cycle.
Fig. 27. Schemat ic diagram of t he MWB melt cryst allizat ion process.
BI BLI OGRAPH Y
" Cryst allizat ion," in E CT 1st ed., Vol. 4, pp. 619636, by A. Ralph Thompson, Universit y of Pennsylvania; in E CT 2nd ed., Vol. 6, pp.
482515, by J. W. Mullin, Universit y of L ondon; in E CT 3rd ed., Vol. 7, pp. 243285, by J. W. Mullin, Universit y of L ondon.
1. N at ional Research Council, F ronti ers i n Chemi cal E ngi neeri ng: Research N eeds and Opportuni ti es, N at ional Academy Press, Washingt on,
D .C., 1988, Chapt . 3.
2. R. M. Felder and R. W. Rousseau, E l ementary Pri nci pl es of Chemi cal Processes, 2nd ed., John Wiley & Sons I nc., N ew York, 1986.
3. R. H. Perry and D . W. Green, eds., Perry' s Chemi cal E ngi neers' H andbook , McGraw-Hill Book Co., I nc., N ew York, 1984, p. 399.
4. H. Charmolue and R. W. Rousseau, A I ChE J. 37, 1121 (1991).
5. J. W. Mullin, Crystal l i zati on, 2nd ed., CRC Press, Cleveland, Ohio, 1972.
6. H. A. Miers and F. I ssac, in H. E. Buckley, Crystal G rowth, John Wiley & Sons, I nc., N ew York, 1951, p. 7.
7. A. D . Randolph and M. A. L arson, T heory of Parti cul ate Processes, 2nd ed., Academic Press, I nc., N ew York, 1988.
8. J. Garside and Roger J. D avey, Chem. E ng. Commun. 4, 393 (1980).
9. M. A. L arson, A I ChE Symp. Ser., 80(240), 39 (1984).
10. M. W. Girolami and R. W. Rousseau, I nd. E ng. Chem. Process D es. D ev. 25, 66 (1986).
11. C. Y. Sung, J. Est rin, and G. R. Youngquist , A I ChE J. 19, 957 (1973).
12. R. E. A. Mason and R. F. St rickland-Const able, T rans. F araday Soc., 62(pt . 2), 455 (1966).
13. D . P. L al, R. E. A. Mason, and R. F. St rickland-Const able, J. Cryst. G rowth 5, 1 (1969).
CRYSTALLIZATION Vol 7
Kirk-Othmer Encyclopedia of Chemical Technology (4th Edition) 32
14. N . A. Clont z and W. L . McCabe, Chem. E ng. Prog. Symp. Ser. 67(110), 6 (1971).
15. R. W. Rousseau and W. L . McCabe, Paper presented at the W orl d Congress on Chemi cal E ngi neeri ng, Amst erdam, June 1976.
16. R. C. Bennet t , H. Fiedelman, and A. D . Randolph, Chem. E ng. Prog. 69(7), 86(1973).
17. P. A. M. Groot scholt en, L . D . M. v.d. Brekel, and E. J. deJong, Chem. E ng. Res. D es. 62, 179 (1984).
18. J. Garside and M. B. Shah, I nd. E ng. Chem. Process D es. D ev. 19, 509 (1980).
19. C. Y. Tai, W. L . McCabe, and R. W. Rousseau, A I ChE J. 21, 351 (1975).
20. C. Y. Tai, J.-F. Wu, and R. W. Rousseau, J. Cryst. G rowth 116, 294 (1992).
21. J. W. Mullin and C. L . L eci, Phi l . M ag. 19, 1075 (1969).
22. P. M. McMahon, K . A. Berglund, and M. A. L arson in S. J. Jan; i: and E. J. deJong, eds., Proceedi ngs of the 9th Symposi um on I ndustri al
Crystal l i zati on, Elsevier, Amst erdam, The N et herlands, 1984, p. 229.
23. R. M. Ginde and A. S. Myerson, J. Cryst. G rowth 116, 41 (1992).
24. J. Garside, A I ChE Symp. Ser. N o. 240, 80, 23 (1984).
25. R. F. St rickland-Const able, Ki neti cs and M echani sm of Crystal l i zati on, Academic Press, I nc., N ew York, 1968.
26. M. Ohara and R. C. Reid, M odel i ng Crystal G rowth Rates from Sol uti on, Prent ice-Hall Press, Englewood Clif f s, N .J., 1973.
27. W. K . Burt on, N . Cabrera, and F. C. Frank, Phi l os. T rans. R. Soc. L ond. 243(A866), 299 (1951).
28. J. R. Bourne, A I ChE Symp. Ser. N o. 193, 76, 59 (1980).
29. W. L . McCabe, I nd. E ng. Chem. 21, 30 (1929).
30. E. T. Whit e and P. G. Wright , CE P Symp. Ser. 67(110), 81 (1971).
31. J. Garside and S. J. Jan; i: , Chem. E ng. Sci . 33, 1623 (1978).
32. A. H. Janse and E. J. de Jong in E. J. de Jong and S. J. Jan; i: , eds., I ndustri al Crystal l i zati on ' 78, N ort h-Holland, Amst erdam, The
N et herlands, 1979, p. 135.
33. A. H. Janse and E. J. de Jong in J. W. Mullin, ed., I ndustri al Crystal l i zati on, Plenum Press, N ew York, 1976, p. 145.
34. M. W. Girolami and R. W. Rousseau, A I ChE J. 31, 1821 (1985).
35. K . A. Berglund and M. A. L arson, A I ChE Symp. Ser. N o. 215, 78, 9 (1982).
36. A. D . Randolph and E. T. Whit e, Chem. E ng. Sci . 32, 1067 (1977).
37. C. Y. L ui, H. S. Tsuei, and G. R. Youngquist , Chem. E ng. Prog. Symp. Ser. 67(110), 43 (1971).
38. H. J. Human, W. J. P. van Enckevork, and P. Bennema in J. J. Jan; i: and E. J. de Jong, eds., I ndustri al Crystal l i zati on 81,
N ort h-Holland, Amst erdam, The N et herlands, 1982, p. 387.
39. K . A. Berglund, E. L . K auf man, and M. A. L arson, A I ChE J. 25, 867 (1983).
40. K . E. Blem and K . A. Ramanarayanan, A I ChE J. 33, 677 (1987).
41. R. C. Z umst ein and R. W. Rousseau, A I ChE J. 33, 121 (1987).
42. N . A. Clont z, R. T. Johnson, W. L . McCabe, and R. W. Rousseau, I nd. E ng. Chem. F undam. 11, 368 (1972).
43. R. C. Z umst ein and R. W. Rousseau, I nd. E ng. Chem. Res. 28, 334 (1989).
44. S. N . Black, R. J. D avey, and M. Halcrow, J. Cryst. G rowth 79, 765 (1986).
45. M. L ahav and L . L eiserowit z in A. Mersmann, ed., Proceedi ngs of the 11th Symposi um on I ndustri al Crystal l i zati on, 1990, p. 609.
46. G. Henning in Ref . 45, p. 113.
47. M. J. Hounslow, R. L . Ryall, and V. R. Marshall, A I ChE J. 34, 1821 (1988).
48. P. Marchal, R. D avid, J. P. K lein, and J. Villermaux, Chem. E ng. Sci . 43, 59 (1988).
49. R. C. Z umst ein and R. W. Rousseau, Chem. E ng. Sci . 44, 2149 (1989).
50. M. W. Girolami and R. W. Rousseau, J. Cryst. G rowth 71, 220 (1985).
51. N . Hiquily and C. L agurie in S. J. Jan; i: and E. J. deJong, eds., I ndustri al Crystal l i zati on ' 84, Elsevier, Amst erdam, The N et herlands,
1984, p. 79.
52. C. Balarew in Ref . 38.
53. S. N . Black and R. J. D avey, J. Cryst. G rowth 90, 136 (1988).
54. K . G. D enbigh and E. T. Whit e, Chem. E ng. Sci . 21, 739 (1966).
55. D . D . Edie and D . J. K irwan, I nd. E ng. Chem. F undam. 12, 100 (1973).
56. A. S. Myerson and D . J. K irwan, I nd. E ng. Chem. F undam. 4, 414 (1977).
57. A. S. Myerson and D . J. K irwan, I nd. E ng. Chem. F undam. 4, 420 (1977).
58. N . Hiquily, C. L agurie, and J. P. Couderc, Chem. E ng. J. 30, 1 (1985).
59. D . H. Jenkins and H. N . Sinha in Ref . 51.
60. R. C. Z umst ein, T. Gambrel, and R. W. Rousseau in A. S. Myerson and K . Toyokura, eds., Crystal l i zati on as a Separati ons Process, A CS
Symp. Ser. N o. 438, 1990, Washingt on, D .C., p. 85.
61. R. C. Z umst ein and R. W. Rousseau, A I ChE Symp. Ser. 83 (253), 130 (1987).
14. N . A. Clont z and W. L . McCabe, Chem. E ng. Prog. Symp. Ser. 67(110), 6 (1971).
15. R. W. Rousseau and W. L . McCabe, Paper presented at the W orl d Congress on Chemi cal E ngi neeri ng, Amst erdam, June 1976.
16. R. C. Bennet t , H. Fiedelman, and A. D . Randolph, Chem. E ng. Prog. 69(7), 86(1973).
17. P. A. M. Groot scholt en, L . D . M. v.d. Brekel, and E. J. deJong, Chem. E ng. Res. D es. 62, 179 (1984).
18. J. Garside and M. B. Shah, I nd. E ng. Chem. Process D es. D ev. 19, 509 (1980).
19. C. Y. Tai, W. L . McCabe, and R. W. Rousseau, A I ChE J. 21, 351 (1975).
20. C. Y. Tai, J.-F. Wu, and R. W. Rousseau, J. Cryst. G rowth 116, 294 (1992).
21. J. W. Mullin and C. L . L eci, Phi l . M ag. 19, 1075 (1969).
22. P. M. McMahon, K . A. Berglund, and M. A. L arson in S. J. Jan; i: and E. J. deJong, eds., Proceedi ngs of the 9th Symposi um on I ndustri al
Crystal l i zati on, Elsevier, Amst erdam, The N et herlands, 1984, p. 229.
23. R. M. Ginde and A. S. Myerson, J. Cryst. G rowth 116, 41 (1992).
24. J. Garside, A I ChE Symp. Ser. N o. 240, 80, 23 (1984).
25. R. F. St rickland-Const able, Ki neti cs and M echani sm of Crystal l i zati on, Academic Press, I nc., N ew York, 1968.
26. M. Ohara and R. C. Reid, M odel i ng Crystal G rowth Rates from Sol uti on, Prent ice-Hall Press, Englewood Clif f s, N .J., 1973.
27. W. K . Burt on, N . Cabrera, and F. C. Frank, Phi l os. T rans. R. Soc. L ond. 243(A866), 299 (1951).
28. J. R. Bourne, A I ChE Symp. Ser. N o. 193, 76, 59 (1980).
29. W. L . McCabe, I nd. E ng. Chem. 21, 30 (1929).
30. E. T. Whit e and P. G. Wright , CE P Symp. Ser. 67(110), 81 (1971).
31. J. Garside and S. J. Jan; i: , Chem. E ng. Sci . 33, 1623 (1978).
32. A. H. Janse and E. J. de Jong in E. J. de Jong and S. J. Jan; i: , eds., I ndustri al Crystal l i zati on ' 78, N ort h-Holland, Amst erdam, The
N et herlands, 1979, p. 135.
33. A. H. Janse and E. J. de Jong in J. W. Mullin, ed., I ndustri al Crystal l i zati on, Plenum Press, N ew York, 1976, p. 145.
34. M. W. Girolami and R. W. Rousseau, A I ChE J. 31, 1821 (1985).
35. K . A. Berglund and M. A. L arson, A I ChE Symp. Ser. N o. 215, 78, 9 (1982).
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62. R. W. Rousseau and R. M. Parks, I nd. E ng. Chem. F undam. 20, 71 (1981).
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Preci pi tati on, L avoisier Technique et D ocument at ion, Paris, 1991.
Ronald W. Rousseau
Georgia I nstitute of T echnology
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