#3.

Acid - Base Titrations 27

EXPERIMENT 3.
ACID-BASE TITRATIONS: DETERMINATION OF
CARBONATE BY TITRATION WITH HYDROCHLORIC ACID
BACKGROUND
Carbonate Equilibria
I n thi s exper i ment a sol uti on of hydr ochl or i c aci d i s pr epar ed, standar di zed
agai nst pur e sodi um car bonate, and used to deter mi ne the per centage of
car bonate i n a sampl e.
An aqueous sol uti on of hydr ochl or i c aci d i s al most compl etel y di ssoci ated i nto
hydr ated pr otons and chl or i de i ons. Ther efor e, i n a ti tr ati on wi th hydr ochl or i c
aci d the acti ve ti tr ant speci es i s the hydr ated pr oton. Thi s speci es i s often wr i tten
H
3
O
+
, al though the actual for m i n sol uti on i s mor e cor r ectl y (H
2
O)
n
H
+
. For
conveni ence we desi gnate i t si mpl y H
+
.
Car bonate i n aqueous sol uti on acts as a base; that i s, i t i s abl e to accept a pr oton to
for m bi car bonate i on.
CO
2-
3
+ H
+
<==========> HCO
-
3
(1)
Bi car bonate i s abl e to combi ne wi th another pr oton to for m car boni c aci d:
HCO
-
3
+ H
+
<==========> H
2
CO
3
(2)
Equi l i br i um expr essi ons for the di ssoci ati on of bi car bonate and car boni c aci d may
be wri tten
K
2
=
[H
+
] [CO
2-
3
]
[HCO
-
3
]
(3)
and K
1
=
[H
+
] [HCO
-
3
]
[H
2
CO
3
]
(4)
wher e K
1
and K
2
ar e the fi r st and second aci d di ssoci ati on constants for H
2
CO
3
;
the exper i mental l y deter mi ned val ues ar e K
1
= 3.5 x 10
-7
and K
2
= 5 x 10
-11
.
When successi ve pr otonati on r eacti ons such as (1) and (2) occur , the extent to
whi ch the fi rst r eacti on pr oceeds before the second begi ns depends on the
28 #3. Acid- Base Titrations
di ffer ence between the two aci d di ssoci ati on constants. By combi nati on of
Equati ons (3) and (4) wi th those for char ge and mass bal ance, [H
+
] can be
cal cul ated for any r ati o of hydr ochl or i c aci d to i ni ti al car bonate concentr ati on,
that i s, at any poi nt on a ti trati on cur ve of car bonate wi th hydr ochl or i c aci d.
Because compl ete and r i gor ous sol uti on i s ti me consumi ng, her e onl y pr ocedur es
for cal cul ati ng the pH at sever al conveni ent poi nts i n a ti tr ati on of 0.1 M sodi um
car bonate wi th 0.1 M hydr ochl or i c aci d (Fi gur e 1) are covered bri efl y. An
anal yti cal textbook shoul d be consul ted for a mor e detai l ed di scussi on of thi s topi c.
pH at Point A in Figure 1. At poi nt A no aci d has been added, and onl y sodi um
car bonate i s pr esent i n sol uti on. The pH i s deter mi ned by the extent of car bonate
reacti on wi th water to gi ve HCO
-
3
and OH
-1
:
CO
2-
3
+ H
2
O <==========> HCO
-
3
+ OH
-
(5)
Her e water acts as an aci d, pr ovi di ng a pr oton to car bonate i on, the base. The
equi l i br i um constant for thi s r eacti on may be wr i tten
K
b
=
[HCO
-
3
] [OH
-
]
[CO
2-
3
]
(6)
Figure 1.
Cur ve for
the ti trati on
of car bonate
wi th hydr o-
chl or i c
aci d.
Mul ti pl yi ng the r i ght si de of Equati on (6) by [H
+
]/[H
+
], we see that K
b
i s equal to
K
w
/K
2
, wher e K
w
i s the di ssoci ati on constant for water .
K
w
= [H
+
] [OH
-
] = 10
-14
at 25C (7)

1
Reacti ons of i ons of a sol ute wi th water often ar e cal l ed hydr ol ysi s r eacti ons. They ar e mor e
pr oper l y consi der ed, however , as si mpl y another exampl e of a Br onsted aci d-base r eacti on i n
whi ch water acts as an aci d or a base.
#3. Acid - Base Titrations 29
and K
2
i s the second di ssoci ati on constant for car boni c aci d [Equati on 3]. I f the
i ni ti al concentr ati on of car bonate and the val ues of K
w
and K
2
ar e k nown, [OH
-
]
can be cal cul ated fr om
K
w
K
2
=
[HCO
-
3
] [OH
-
]
[CO
2-
3
]
(8)
Assume that the equi l i br i um for Equati on (5) l i es far to the l eft, so that the
car bonate i on concentr ati on i s sti l l essenti al l y 0.1 M. Si nce bi carbonate and
hydr oxi de ar e for med i n equi mol ar amounts,
[HCO
-
3
] = [OH
-
] (9)
Substi tuti on of numeri cal val ues and Equati on (9) i n Equati on (8) gi ves
10
-14
5 x 10
-11
=
[OH
-
]
2
0.1
(10)
and
[OH
-
] = 4.5 x 10
-3
M (11)
From Equati on (7)
[H
+
] =
10
-14
4.5 x 10
-3
= 2.2 x 10
-12
M (12)
so the pH i s 11.7.
I n our use of Equati on (6) we assume that the r eacti on
HCO
-
3
+ H
2
O <=========> H
2
CO
3
+ OH- (13)
does not occur to an appr eci abl e extent; that i t does not can be veri fi ed by
substi tuti ng the val ue for [H
+
] found i n Equati on (12) i n Equati on (4) and
30 #3. Acid- Base Titrations
cal cul ati ng [H
2
CO
3
]. I f [H
2
CO
3
] i s found to be gr eater than 5% of the total
car bonate concentr ati on, the [H
+
] cal cul ated fr om Equati ons (6) and (7) wi l l be
appr eci abl y i n er r or . I n thi s case the expr essi on shoul d be sol ved ei ther exactl y,
by i ncl udi ng al l speci es (whi ch i s tedi ous), or by successi ve appr oxi mati ons.
Cal cul ati on shows that [H
2
CO
3
] at Poi nt A i s negl i gi bl y smal l , so our assumpti on
i s val i d. The addi ti onal assumpti on that [CO
2-
3
] i s essenti al l y 0.1 M al so i s
confi r med because Equati ons (9) and (11) show that [HCO
-
3
] i s l ess than 5% of
[CO
2-
3
] .
Note fr om thi s di scussi on that
K
w
K
2
= K
b
, or K
w
= K
2
K
b
. Thus, i f Ka for an aci d
HA i s k nown, K
b
for the cor r espondi ng base A
-
can be cal cul ated i n aqueous
sol uti ons. An aci d HA and base A
-
ar e cal l ed a conjugat e aci d-base pai r ; HA i s
the conjugate aci d of A
-
and A
-
the conjugate base of HA.
pH at Point B. At Poi nt B i n Fi gure 1,
1
2
mol e of hydr ochl or i c aci d has been added
for each mol e of car bonate. The sol uti on now contai ns an equi mol ar mi xtur e of
car bonate and bi car bonate. We can cal cul ate the pH at thi s poi nt by r ear r angi ng
Equati on (3) to
[H
+
] =
[HCO
-
3
] K
2
[CO
2-
3
]
(14)
Si nce the bi car bonate and car bonate concentr ati ons ar e equal , the hydr ogen i on
concentr ati on i s equal to K
2
, and the pH i s 10.3.
Accur ate cal cul ati ons of concentr ati ons of speci es dur i ng ti tr ati ons must i ncl ude
the effect of di l uti on by the ti tr ant, but thus far those caused by the addi ti on of
hydr ochl or i c aci d have not been consi der ed. To cor r ect cal cul ati ons of
concentr ati ons of the major components for di l uti on, mul ti pl y each cal cul ated
concentr ati on by the factor V/(V + ), wher e V i s the vol ume of the or i gi nal
sol uti on and i s the vol ume of hydr ochl or i c aci d added at any poi nt. Al though i n
the present exampl e the effect i s sl i ght, i n many systems the cor r ecti on i s
si gni fi cant.
#3. Acid - Base Titrations 31
pH at Point C. The fi r st equi val ence poi nt (C i n Fi gur e 1) i s r eached when 1 mol e
of hydr ochl or i c aci d per mol e of car bonate has been added. Thi s sol uti on contai ns
onl y sodi um bi car bonate; [H
+
] i s cal cul ated by
[H+] = K
1
K
2
= (3.5 x 10
-7
) (5 x 10
-11
) = 4.2 x 10
-9
M (15)
and the pH i s 8.4.
pH at Point D. Pr otonati on of hal f the bi car bonate gi ves an equi mol ar sol uti on of
bi car bonate and car boni c aci d (Poi nt D). Thi s i s agai n a buffer system, thi s ti me
i nvol vi ng the fi rst di ssoci ati on constant of car boni c aci d. The cal cul ati on i s
handl ed i n the same way as for Poi nt B, wi th K
1
used i n pl ace of K
2
, to yi el d a pH
of 6.5.
pH at Point E. At the second equi val ence poi nt (E) the pH i s deter mi ned by the
extent of di ssoci ati on of car boni c aci d, the pr i nci pal speci es pr esent, and [H
+
] i s
cal cul ated fr om Equati on (4):
K
1
= 3.5 x 10
-7
=
[H
+
] [HCO
-
3
]
(0.1) [50/(50 + 100)]
=
[H
+
]
2
0.033
(16)
Ther efor e,
[H
+
] = 1.07 x 10
-4
M = 10
-3.97
(17)
the pH i s 3.97, or r oundi ng to 2 si gni fi cant fi gur es, 4.0.
Detection of the Equivalence Point
Ei ther the fi r st or second equi val ence poi nt (C or E i n Fi gur e 1) can be used for
car bonate anal ysi s. I n nei ther case i s the pH change l ar ge i n the r egi on of the
equi val ence poi nt. An uncer tai nty of 0.1 pH uni t at ei ther end poi nt r esul ts i n an
uncer tai nty of about 1% i n the amount of hydr ochl or i c aci d r equi r ed. The er r or
can be r educed i f the ti tr ati on i s car r i ed to a pr esel ected i ndi cator col or . When a
sol uti on i s ti tr ated to the second equi val ence poi nt, a better appr oach i s to take
advantage of the di ssoci ati on of car boni c aci d i nto a sol uti on of car bon di oxi de i n
water . Shaki ng or boi l i ng a sol uti on of car boni c aci d causes the equi l i br i um to be
H
2
CO
3
<=========> H
2
O + CO
2
(g) (18)
32 #3. Acid- Base Titrations
dr i ven to the r i ght thr ough l oss of car bon di oxi de. I f a car bonate or bi car bonate
sol uti on i s ti tr ated to just befor e the equi val ence poi nt at pH 4 and then shaken or
boi l ed,
2
the pH wi l l r i se to about 8 as the concentr ati on of car boni c aci d dr ops
(dotted l i ne i n Fi gur e 2). The pH i s no l onger contr ol l ed by di ssoci ati on of a
r el ati vel y l ar ge concentr ati on of car boni c aci d but by a smal l concentr ati on of
bi car bonate. When the ti tr ati ons conti nued, the pH goes down shar pl y because
the amount of car boni c aci d for med i s smal l and the buffer i ng effect negl i gi bl e
(dashed l i ne i n Fi gur e 2).
Standard Solutions
Some standar d sol uti ons can be pr epar ed di rectl y by wei ghi ng or measur i ng
car eful l y a defi ni te quanti ty of a pur e substance, di ssol vi ng i t i n a sui tabl e sol vent,
and di l uti ng i t to a known vol ume. None of the str ong aci ds, however , i s
conveni ent to handl e and measur e accur atel y i n concentr ated for m. Ther efor e a
sol uti on of appr oxi matel y the desi r ed mol ar i ty i s pr epar ed, and the exact val ue i s
deter mi ned by standar di zati on agai nst a pr i mar y-standar d base.
Fi gure 2. Effect of
r emoval of car bon
di oxi de on pH
change the second
equi val ence poi nt
i n a ti trati on of
car bonate wi th
hydr ochl or i c aci d.
Band i ndi cates
r egi on of change
of i ndi cator col or .
Pr i mar y standar ds are stabl e, nonhygr oscopi c substances that r eact
quanti tati vel y and ar e easy to pur i fy and handl e. A hi gh equi val ent wei ght i s
advantageous because wei ghi ng er r or s are mi ni mi zed. Among the excel l ent
pr i mar y standar ds avai l abl e ar e potassi um aci d phthal ate, benzoi c aci d, oxal i c

2
I n mammal s the CO
2
pr oduced thr ough bi ol ogi cal oxi dati on i s car r i ed by the bl ood to the l ungs,
where i t i s exchanged for oxygen. Part of the CO
2
i s present i n the bl ood as H
2
CO
3
. Si nce the ti me
avai l abl e i n the l ungs for exchange i s shor t, the di ssoci ati on of H
2
CO
3
to CO
2
and H
2
O i s
accel er ated by the enzyme car boni c aci d anhydr ase, a zi nc-contai ni ng pr otei n of hi gh mol ecul ar
wei ght. Thus natur e need not r esor t to ei ther boi l i ng or shaki ng.
#3. Acid - Base Titrations 33
aci d di hydr ate, and sul fami c aci d for standar di zi ng bases and sodi um oxal ate,
tr i s(hydr oxymethyl )ami nomethane, 4-ami no pyr i di ne, and sodi um car bonate for
standar di zi ng aci ds. Pur e anhydr ous sodi um car bonate, besi des havi ng al l the
pr oper ti es of a sui tabl e pr i mar y-standar d base, has the added advantage i n thi s
exper i ment of bei ng the same compound as the substance deter mi ned. Thi s tends
to compensate for deter mi nate er r or s i n end-poi nt sel ecti on.
PROCEDURE
Reagent List:
Unknown Sampl e - must be mi xed thor oughl y and dr i ed
HCl concentr ated - appr ox. 12M
sodi um car bonate (Na
2
CO
3
) - must be dri ed
Br omocr esol Gr een - i ndi cator
Put a l i ttl e l ess than 1 l i ter of di sti l l ed water i nto a cl ean 1-l i ter bottl e. Cal cul ate
the vol ume of 12 M HCl r equi r ed to pr epar e 1 l i ter of 0.2 M HCl , and measur e thi s
quanti ty i nto a smal l gr aduated cyl i nder . Tr ansfer i t to the bottle and mi x
thor oughl y. Label .
Standardization of HCl with Primary-Standard Na
2
CO
3
Dry 1.5 to 2.0 g of pure Na
2
CO
3
i n a gl ass wei ghi ng bottl e or vi al at 150 to 160C for
at l east 2 hr .
3,4
Al l ow to cool , i n a desi ccator i f necessar y, and then wei gh by
di ffer ence (to the near est 0.1 mg) thr ee or four 0.35 to 0.45 g por ti ons of the dr y
mater i al i nto cl ean 200-ml coni cal (Er l enmeyer ) fl asks. Add about 50 ml of
di sti l l ed water to each and swi r l gentl y to di ssol ve the sal t. Add 4 dr ops of
br omocr esol gr een i ndi cator and ti tr ate wi th the HCl sol uti on to an i nter medi ate
gr een col or . At thi s poi nt stop the ti trati on and boi l the sol uti on gentl y for a
mi nute or two, taki ng car e that no sol uti on i s l ost dur i ng the pr ocess. Cool the
sol uti on to r oom temper atur e, wash the fl ask wal l s wi th di sti l l ed water fr om a
wash bottl e, and then conti nue the ti tr ati on to the fi r st appear ance of yel l ow. Just

3
Na
2
CO
3
tends to absorb H
2
O fr om the ai r to for m Na
2
CO
3
.H
2
O, and CO
2
to for m NaHCO
3
. At
l east sever al hour s of dr yi ng at 140C i s necessar y to r emove al l H
2
O and CO
2
.
4
Use a penci l or fel t marki ng pen to l abel the contai ner wi th the name or sampl e number of the
contents and wi th your l ocker number . The contai ner may be pl aced i nsi de a smal l gl ass beaker ,
and a watch gl ass, r ai sed wi th sever al bent por ti ons of gl ass r od, pl aced on top for pr otecti on.
Avoi d l eavi ng chemi cal s or equi pment i n the dr yi ng oven l onger than necessar y, thi s not onl y
causes cr owdi ng, but i ncr eases the chance of equi pment bei ng br oken or sampl es contami nated by
spi l l ed chemi cal s.
34 #3. Acid- Base Titrations
befor e the end poi nt the ti tr ant i s best added i n fr acti ons of a dr op.
5
Recor d the
bur et r eadi ng and add to i t the bur et cal i br ati on cor r ecti on.
Cal cul ate the mol ar i ty of the HCl sol uti on. The pr ocedur e outl i ned i n the
di scussi on of cal cul ati ons bel ow may be used as a gui de. Rel ati ve devi ati ons of
1
i ndi vi dual val ues from the average shoul d not exceed about 2 parts per 1000.
Determination of Carbonate in a Sample
Mi x the sampl e VERY THOROUGHLY and then dr y i t i n a wei ghi ng bottl e or
smal l beaker for at l east 2 hour s at 150 to 160C. Wei gh i nto cl ean 200-ml coni cal
fl asks, to the near est 0.1 mg, 0.35 to 0.45 g sampl es and ti trate as i n the
standar di zati on pr ocedur e.
Cal cul ate and r epor t the per centage of Na
2
CO
3
i n the sampl e. Use the Q test as
the cr i ter i on for r ejecti on of suspect exper i mental data. Ei ther the medi an or the
aver age may be r epor ted. When the medi an i s chosen the medi an val ue for the
mol ar i ty of the HCl shoul d be used i n the cal cul ati ons r ather than the aver age
val ue.
CALCULATIONS
The per centage of Na
2
CO
3
i n a sampl e can be cal cul ated i n two steps: (1) the
deter mi nati on of the mol ar i ty of the HCl ti trant fr om the standar di zati on
ti tr ati ons and (2) the cal cul ati on of the per centage of Na
2
CO
3
fr om ti tr ati ons of the
sampl e.
1. Mol ar i ty of HCl . I n ti tr ati ons of Na
2
CO
3
wi th HCl to the pH 4 end poi nt, 2
mol es of HCl ar e added for each mol e of Na
2
CO
3
:
2HCl + NaCO
3
<=========> H
2
CO
3
+ 2NaCl (19)
The HCl mol ar i ty i s obtai ned fr om the fol l owi ng r el ati ons:
MHCl =
mol es HCl
l i ter
=
mol es Na
2
CO
3
x 2
(ml HCl /1000)


5
To del i ver amounts l ess than 1 drop from a buret, fi rst l et a dropl et form on the ti p, and then touch
the ti p momentar i l y to the i nsi de wal l of the fl ask. Ri nse the wal l wi th a smal l amount of di sti l l ed
water from a wash bottl e to ensure that the ti trant i s washed i nto the sol uti on. Do not ri nse the ti p of
the buret.
#3. Acid - Base Titrations 35
(20)
=
(wt of Na
2
CO
3
) x 2
(mol wt Na
2
CO
3
) (ml HCl /1000)

The factor 2 r equi r ed because each mol e of Na
2
CO
3
r eacts quanti tati vel y wi th
2 mol es of HCl .
2. Per centage of Na
2
CO
3
i n Sampl e. The per centage of Na
2
CO
3
i n the sampl e i s
cal cul ated as fol l ows:
%Na
2
CO
3
=
wt of Na
2
CO
3
i n sampl e
g sampl e
x 100
=
(mol es Na
2
CO
3
)(mol . wt. Na
2
CO
3
)
wt of sampl e
x 100 (21)
=
(ml HCl ) (mol ar i ty HCl ) (mol wt Na
2
CO
3
)
1000 x 2 x wt. of sampl e
x 100
Remember: Poor r esul ts ar e often caused by er r or s i n cal cul ati on r ather than
by faul ty l aboratory techni que. Check al l cal cul ati ons before
r epor ti ng r esul ts.