‘A study of reaction rates (chemical kinetics) aioves us 0
teactions work. You cannot deduce a reaction mechanism secon
rd Banced ceric equation pine wot cctcree nd
leads to the rate equation, which, in turn, leads to 1 e reaction mechanian
(Gee page 12) oe
change in concentiation ge
time eat
tad exactly how,
rate of reaction
Rate equations
Rate equations show the relationship between the rate and the powers to which
‘eactant concentrations are raised. If two reactants, A and 8, react together ma
‘measurements of reaction rates with different concentrations of A and B (se ba
ould give the rate equation r
rate = HAMEY
In this case:
'¢ isthe rate constant, which is constant ata particular temperature
‘+ [A] and [8] are the concentrations of substances A and 8
‘© 15 the order with respect to A, and y's the order for 8
‘© The overall order of reaction is the sum of the individual orders, x + y.
‘Studies of some reactions gave the following rate equations:
a rate = b rate = KAp(B)
© rate =| d rate = KAI}
Which reactions have the same overall order, and which rate i independent of
_the concentration of one reactant?
_ Reactions a,b are both third order overall Reaction b is zero order wth
respect to reactant A, and so its rate is not affected by varying the amount of
feactant A We can wate rate = HB)"
Measuring reaction rates
ute = HAl-thg Rate of reaction are measured by monitoring he
Ghesastraghtine fate of change of an observable property.
# Colorimetry measures the intensity ofa colour
in a reaction mixture with time, such asin the
‘oxidation of iodide ions to give brown ‘odne
In clock reactions the reaction i timed unt 2
faye = Hap ex1 sudden colour change happens when acetan
— the te doesnot amount of product is formed.
depend on (A [Mass change is used when a gas is produced
For example, when calcium carbonate reacts
with acids to release carbon dioxide the mass 0!
the flask decreases
Volume change is an alternative to mass
changes for gases. For example, magnest™
reacts with acids to release hydrogen, whic
be collected in a syringe.
a Titrimetric analysis uss titrations to mes"
How the reaction rote wares forthe concentration of for zr, fst rd changing concentrations of a reactant
3 " ‘0 product —for example, the fall in 204
‘oncentration during estetfication Activation energy and catalysis
When reactant molecules collide, it may resuitt erica ‘
energy requirement before this can happen. The activation energy
‘energy needed by reactant particles (molecules or ‘ons bef
be
Aeacton pathway for an exothermic reaction
The diagram shows that the reaction is:
© exothermic ~ the products are at a lower energy level than the reactan
‘© subject to an energy barrier, the activation energy, in route 1
'* able to follow an alternative pathway in route 2, with a lower barre
A catalyst increases the reaction rate by providing an alternative reaction
with a lower activation energy. Such catalysed reactions are fa
Catalysts and reactants can be in the same physical state, called homogeneou
= for example, all liquids. Or they can be in diferent states, when the
heterogeneous.
loner Ome | exhaust gases Patou
Bec
Contact process
Suture cco | Sulfur dioxide, oxygen
manufacture | oeses
Esterication | Soktions Of acid,
| akohol Hydeogen ir
} sear ee
Many catalysts are transition metals (or their compounds)
because t
‘oxidation states and can alter the numbers of bonds avai
lable to x
weet be mea
Soest Th atone we
coe molecules, which reduces the actwation energy for :
Frame of hetersgenecus catahass
£2 Chemise Reson Guide ent
Mechanisms and rate-determining ES tet
rate-determining step.
Nucleophilic substitution mechanisms
halogenoalkanes
tution mechanisms are possible when an iodoalkane reacts
R—-1+ OH R—OH +1
fate data can show which mechanism actually takes
Ze
Ho—¢
\
substitution of a primary halogenoalkane
‘+ The single step ilustrated for the substitution of 1-iodopropane, a primary
halogenoaikane, involves two different species - both the hydroxide ion and t
primary halogenoalkane
*_ The reaction will be second order — it depends on the concentration of both the
hydroxide ion and the primary halogenoalkane.
So, rate = KRI[OH-}
We call this an Sy2 mechanism, meaning substitution/nucleophilie/second order
Tertiary halogenoalkanes hydrolyse by the alternative $1mechanism, meaning
Substitution/nucleophilic/first order.
determining
Mucleophiic substitution of tents halegencaltane
* The C— halogen bond breaks fist (stow step) followed by attack by the hydroxide
ion (fast step),
* The slow step involves only one species and does not depend on the concentration
of hydroxide ions. Hence the reaction is first order overall
rate = K{Ri)
A2 Chemistry Revision Guide Experiment intsal concemvanon hoeub conceneaniet eas cme om
of Aime! om of Bmw om Ty
Seed
‘Initial concentration | Initial concentration | Initial rate/moldm °s* |
of A/moldm? =| of B/mol dm >
00 x 10
i fers of reaction with respect 19 and to B, 8)
i Write the rate the reaction 0
it Calculate the k action using the results from experiment 3. State its units |
ai |
Looking at experiments 1 and 2, as concentration of B doubles, the rate increases four times so the reaction is second order with
Looking at experiments 1 and 3, as concentration of A doubles, the rate doubles so its first order with respect A. (1) |
You must indicate thatthe concentration of one of the reactants stays the same forthe pair of values chosen for comparison to gain the
third mark, (1)
Therate equation is ate = MAIBF (1)
Note that this now presents the same information 2s (ai in cifferent form. your values for (ai) ae wrong, say both second
corde, but the rate equation in (a)(i) matches theses values, you may still et the consequential marks
it b= 195 X 10-¢maldm=25-1_
7000 mol d=? x {0.100 mol dm
=01%5 1) dmémol-?s-" (1)
‘Answers to three significant figures would be appropriate with this data but examiners may not insist on this in awarding marks. |
‘A.common errar isto ignore the instruction in the question to calculate the value of k for experiment 3
b Boplain in terms of coli
12ry, why the rate of reaction increas
3 with an increase in temperature. @
There are 3 marks available here so think about saying three distinct things. Note that this question also tests knowledge from AS Unit 2.
‘© Increasing the temperature means that molecules collide with greater energy. (1)
‘+ This means that a greater proportion of the colliding molecules will have energy equal to or greater than the activation energy, the
minimum required. (1)
'* Consequently @ greater proportion ofthe collisions willbe successful and result in reaction occurring. (1)
Suetue your answer wih separate lines or bullet pont s that the examine can see immediately that you are making separate points in
your answer Avoid lengthy prose where the danger is that you will repeat yourself and fail to gain full marks
(From Edexcel Unit test 502, June 07) ‘si
ob
| A
B
c
o
A
B
c
.
2 Inaque
Pret Ty
PSRs CUCL
olution, propanone and bromine react as follows
CH;COCH;(aq) + Br,{aq) > CH,COCH,Brlaq) + HBriaq)
ve 2
‘This reaction is zero order with respect to bromine. What can we deduce from this’
The slowest step involves bromine
The rate of reaction has a constant value
Bromine is a catalyst
Choose the correct response
Bromine is not involved in the fate-determining step
The slow rate-determining step cannot involve the bromine because itis zero order. The answer is D.
fate = k{2. bromo-2-methylpropane}
What is the first st
fi
Breaking
This compound reacts by an Sy
Check that you
‘their stability
aN explain the
0s, This
fep in the reaction me
ectrophilic attack by hydroxide ior
of the C— Br bond Produ
The CBr bond breaks as the
Nucleophitic
icing a carb
attack by hydroxide ions on the
| mechanism to give 4
‘differences between 5
$8 Common question
()
lechanism? Choose the Correct response:
ns on the C— Br bond
jocation
C—O bonds forms
“atbon in the C— Br bond
Stable carbocation, The answer is B ()
wnt
ill
co
1 mechanisms and §y2 Mechanisms in terms of how easily carbocations
Pr iu te sane non of sigfcart
ores yor intact rem
a bese wt tay a or
Marks way be at 4928
nagpnpate cute ot sapticen
a beeen emia sact0n 08
9 treatin of too hes 3.
4 OMG + 2A) m= Dig, 00
pe canon eeron erp te
‘seactin set be S y20 get
i santas een ge,
‘of disorder in a system. YOU can al
. eee zero at zero kelvin (absolute zer
fs the temps
A fature of a material inc
As ip increases, Higher temperature
1e to greater distance between
ore ordered than the same ions disolveq
s the entropy to increase.
mber of particles increases.
‘Change in the
entropy
d | Posie (increasing |
entropy)
Negative
reducing te
fr resulting from a process, the more likely the process, The
Calculating changes in entropy, AS
Entropy values depend on temperature and physical state. Entropy values also increase
2s the complenty of a substance (the number of bonds) increases. For example, the
entropy of ethanoxc acd (CH,COOH) is greater than that of methanol (CH,OH).
A standard entropy 5 the entropy of a substance at standard temperature and
pressure, and is expressed per mole of substance.
‘The standard entropy change for physical or chemical processes isthe differencen |
the entropies of the products and reactants measured under standard conditions
ASirum = ESpotcs ~ ES |
pM
‘Calculate the standard entropy change for the thermal decomposition of
Explain your answer. eS
7 [aCOys) + Ca0[s) + CO, |
Seeeencek imo: 48zy ae) yates |
Troe of aed a the entropy change shows thatthe entropy increases fact |
‘aloum carbonate produces 1 mole of gas, with greater sort. |
$5 * Stoten ~ Stay |
AS = G9.73K-? mot co |
= $3601K mag oak) 8295K°' mol? } |
italia tg :
| sti ned eno ta ocala =
t sa ad w= mtcoyns case eco
Feasibility, stability and inertness
A feasibe eachon has 35.oy > 0, Because AS
he value of As,
reaction that does not happen at
Magnesium turnings react with dilute sulfuric acid to release hydrogen ga:
A te meg wwe #8 The temperature ofthe acid rises considerably. Explain why this reaction is
ci Cs tt tno spontaneous at room temperature ae
Siaienansateeoeeone The reaction exothermic so the term AM wil have @ negative value. The
hath tpapuida copeet lah ‘metalic lattice of magnesium metal is destroyed as it reacts with the aci,
: ¢ ‘producing free ions in solution and a gas. This means that the entropy of the
——tieneores System increases ~t has a posite vale, and this reacton is spontaneous
The decomposition reaction given on the previous page:
CaCO\6) = Ca0(s) + CONG)
oes not occur at room temperature
= 7 SN Gwen the standard enthalpy change for the reaction, AH® = +178kimol”,
‘iculate the lowest temperature at which this reaction becomes feasible.
Pre secs of SMa geen otal AS ame Can be calculated as before.
ed hn wits of AS oe gies AS = So se
Jet! You ree camer tJ by toes . Ee
: e a (39.7 )K-' mol! + 213.6)K-" mol") ~ 92.9)K-' mol)
ee eee le +160.41K-* mol"?
the absclate peste K oe
| ee a
ane
FOF AS cas > 0, ASham > AE
178 x 10°) mol-*
T> Sx 30'mol > 1110 @ sig. figs)
Stability and inertness and the
activation energy
Some reactions are puzzling because they are highly exothermic but are not
Spontaneous at room temperature. An example is that a mixture of methane
and oxygen gases does not ignite spontaneously at room temperature
There are different kinds of stability that can affect chemical reactions. The
thermodynamic stability of 3 compound relative to its elements depends
‘on the enthalpy level of the products relative to the reactants, The diagram
{left for an exothermic reaction shows an example of products that are
‘thermodynamically more stable than the reactants. A negative enthalpy of
formation indicates that a compound is more stable than its elements it
‘must form exothermicaly from its elements, stability and inertness
Afeasible reaction has ASqu > 0. Because AS ox = ASipuon ~ AH, the key factors for
the feasibility of a reaction are.
‘© the entropy change in the system, ASypen
{the temperature measured in ken
{the enthalpy change with the surroundings, AH.
Spontaneous reactions can only happen fot ASyy > 0. The value of AS... deperus
‘on temperature. This s why a chemical reaction that does not happen at room
temperature may become feasible a Tincreases
‘You vl get the wrong answer if you The temperature of the acid rises considerably Explain why this reac
se Celis instead af kevin these ‘spontaneous at room temperature
‘alultions. Remember tat Coleus ‘
emperatues can have oagatv values
tut kelvn temperatures carat Kelun
‘empeatires start at absolute zero and
‘necessary have postive values
“The reaction is exothermic so the term AH will have a negative value. The
‘metalic lattice of magnesium metal is destroyed as it reacts with the aco,
pptoducing free ions in solution and a das, This means thatthe entiopy of the
System increases ~ it has a positive value, and this reaction is spontaneous
‘The decomposition reaction given on the previous page
CaCOsls) + C2069) + COx(9)
does not occur at oom temperature
weed Given the standard enthalpy change for the reaction, 4!” = + 178k) mo!
Calculate the lowest temperature at which this reaction becorves‘easible
The unis ef AMarogven nk) mal
aad th nts Sar gen n
na You eed to canver 0 :
er aise ne yanre = @9.7JK-!mol’! + 213 6)K-! mol-*) ~ 929
upg by 100. Now aloha Fis mol +
‘the absolute temperature, K. Se tAEDA TK.” not
i J MSua = ASpecn ae
For AS cus > 9, ASirn > AE
178 x 108) mol"!
160.41"? mo}
35m C2N De Calculated a before
Symon = Spas ~ Staats
T> > ITOK G sig figs)
Stability and inertnes ne
activation energy
\ Some reactions are puzzling becaus
scmaton _spOntaneous at room temperature, An ex af me
| feet ‘and oxygen gases does not ignite spo mpe
eed There are diferent kinds of stabil
\ Waray bay ofa conpour
\
‘0n the enthalpy level of the products relat
\ eraducts (left) for an exothemnc reaction show
thermodynamically more stable than the rea
formation indicates that a c
‘must form exothermicaly from its elem ‘Wien ionie solids, such es sodium chloride, dissolve ina polar solvent, there ax:
"separate enthalpy terms from two separate processes:
Siattice eneray ~the solid must separate into individual ons to dissolve (an
‘endothermic change).
‘= hydration enthalpy - the separated ions interact with the surrounding pol
solvent, such as water (an exothermic change)
‘The enthalpy of solution of an ionic compound is:
Ben = —AHanc my + SH
When 3 new lattice forms from gaseous ions, energy is released in an exothermic
[process = thisjs the lattice energy, When a crystaline material dissolves, the overs,
‘An amaunt of eneray numerically equal tothe lattice eneray must be
to break the crystal and separate the rons. This is an endothermic process
‘Harm Can have a positive or a negative value
# A positive AHsinos Corresponds to an overall endothermic change - dissolving
favoured. femay stil be favoured by an increase in entropy Solid sodium chic
Isa highly ordered 3-D lattice with a low entropy value On dissolving, the
Separate and move independently, the entropy of the system therefore nese
favouring the change
4 A negative BPin9, Comtesponds to an overall exothermic change and so d
i5 favoured in terms of enthalpy. The products have less energy than the
General, although dissolving is regarded as a physical not a chemical cha
lithium chioride
Sodium chloride
Silver chlonde
‘Magnesium sulfate
oo > BH,
isnegative However, solids with an
ge is positive enaugh to overcome the 7
MIE ~12, AS... can be > 0
"ill dissolve ot 298K because
Iwill not cissolve at 298K because
Calculating enthalpy of hy<'ration or
solution from Hess cycles
‘The standard enthalpy of hydration
mole of the gaseous ions is hydrated (int
where further dilution would cause no furt!
infinite dilution. For example’
Na“(g) + 2 Inue but the rate of the forward reaction is equal to the rate of the
this is called a dynamic equilibrium. A reaction may only obtain
ina closed system, in which both reactants and products are sealed in
HAg) + h(g) = 2HIg)
en and iodine gases are first mixed in a closed system, the forwarc
valone begins since there are no products present. As the amounts
d rate decreases. Once some product malecvies have been form
jon can begin, The tate of the reverse reaction increases until
tions are happening at the same rate. Ths isa dynamic equilibrium (at
perature)
Can also result in dynamic equilibria, For example, iodine in a seae
PB ‘steady temperature sublimes in a solid-vapour equilibrium
16) =o)
ules leave the sold phase and enter the vapour phase atthe same a
from the vapour phase and enter the solid phase
al reactions that are reversible include
acess for ammonia ~ N,(q) + 3H,(a) = 2NH,
for sulfuric acid - 250,09) + 0,69) = 2
for example CHCOOH() + C;H.OHI) = CH.
concentrations
‘between the reactant and the produc
‘a particular temperature. This is called the equilibrium law
dine fer. above:
= equim constant expressed in terms of concentrator
concentrations with unis of mold” The
values, not the intial concentration values.
‘terms are raised to the powers that correspond tot el is systems
have been homogeneous ~ al iquids or
‘more than one physical state i present. For
Healelm carbonate, calcium oxide and carbon dioxide gas
CaCO,9) = C2019) + Coy)
i ICaC0,65)) Mary stents ose mars by wrong
‘The concentration of solids are always taken to be constant. This simplifies the ing sold mth expen cK
«expression for the equilibrium constant to: aes
¢ © Ke = {COxg)
Understanding the meaning of K. values
‘= 11K. 1 means thatthe products are favoured, andthe postion of equinus lies
well over to the product side. ;
* If K. <1 means that the reactants are favoured, and the position of equilibrium lies
well over tothe reactant side, ‘
+ IK isvery
| a5 1 % 10; this means that the reaction has gone Gaseous equilibria and K,
With gaseous equilibria, it sometimes makes more sense to use an equilibrium co
expressed in terms of pressure rather than concentration,
You need to be clear about the meaning of the term partial pressure of a gas in
‘mixture Partial pressure can be defined as the pressure a gas would exert if al
filed the container
‘Partial pressure is used for mmxtures of gases that do not react together chemica
‘= We assume that each gas behaves independently in the gas mixture
«The total pressure of the moture is the sum of the partial pressures of each ga,
this s Dalton’s law of oartal pressures.
‘+ Partial pressure s defined in terms of mole fractions. For a mixture of two 4:
and 8,
= _fumber of moles of A
the mole fraction of a = — number of moles of A
the partial pressure of A = mole fraction of A X the total pressure of the
ERE
For a mixture involved in the Haber process, calculate the mole fractions anc
arial pressures of each gas The midure contains 249g ammonia, 60 23
‘trogen and 13.1.g hydrogen at a total pressure of 10 atm,
Nila) + 3H,(9) = 2NHAQ)
Coa
Caer
eck that the sumo he roe |
taser Tewiesotin | SEE the mabe ito mls, rl the calculate the mole ac
i ‘good een ayeement, number of moles = —.
\ [canteen oceans fumbles of moles are ammona 1.46, nitrogen 2.15, drogen 6 +
whlpearanrgeer tian | Qiveg aot ot 1016
mame =Stmn | moe tacton ammonia = 148 <9 1g
mmole fraction nit = 21s -
vogen = 2180.21
mole fraction hydrogen. = $e = 068
a Pressure units
Coen ‘Gas pressures can be expressed in
* atmospheres (atm)
Nolet agultiavantewriten || * mmHg
thr 04 Hal + dle 2g) | Standard mesures taken as 101 kPa
|
‘a vanety of units:
+ kPa (1
Nm?
ZH) = Hi + hd bt wt
ove doers
a ae Sel K, fora homogeneous system
teat acheeer ee forthe equlboum HQ) + Ifa) = 2K)
Sp Me equllsrium constant in terms of partial pressures
K, = Plt :
BR) x pp
he powers that corres
Note the ind
moles in the ee
balanced equation, een
Compare this with
ys wea bracer hat
Ste samernacteiecertag | The Opresions fr x
es feet cya | MeSECndnes
ei measured at equilib
(ase, K, has no units
are for K. are similar — the frst
concentrations. To
IM. AS with K., the ur
alclate Kal paral presse
ts fK, depend on the ener
sty Revision Guide
| More on eq
‘rasteldbe alec 9
~ voor tm equiv crt fo 8
mtn tases on ht dese roman
gett. sch sith preparation
‘ofan erm
ey
yaar only gente amount fae
of esses in te aque
moni, youcan stl wen otthe |
ruber of oles eather eats |
| ae rs a he stoeomeny
(eve lero) oft econ
Feet o conver rambo of mois
ts conearratons inte equim
constat eprecsion Usa,
areal tinh abe sok
Sues show th sep een yo ik
|
she voRmes wif cancel out |
uilibrium constants
Calculating K, from exper! imental data
‘Alcohols eact reversibly with carboxylic acids to give esters
‘acid + alcohol ~ ester + water
“The reaction can be catalysed by hydrogen ions. Usually, a small amount of
Concentrated sulfunc acid supples the catalyst. A common example of the
estenfication reactions:
ethanoic acid + ethanol = ethyl ethanoate + water
Inestefcaton, the amounts of substances present can be found using tat
1 She concertavon of he estat ac falas he reacton proceeds
+ When te acu concentration costa, equibrium hasbeen established sh
temperate
«Tsing 825 dcr sample wth standard sodum yaroxde solution and an
Indesor gues the concentaon ofa present tequliorum
«Knowing he tl amounts of ocd and skool al four ofthe equilib
Concentaton canbe eacuted using the balanced equation Using the ecu
meeson gress vole fr K,
Equilibrium constants for esterification are often close in value to 1. This would
‘poor yield ofthe ester Yields can be improved by
+ adding an excess ofthe alcohol this shifts the position af equllisnum in f2vou
the ester product
‘© recovering unused alcohol atthe end by distillation and re-using it
Equitbnium is attained after several hours when these mixtures are heated
bath at constant temperature
SET =
At 323K (50°C) a mixture of 0 Smol ethanol and 1.0 mol ethanoie
feacted until equilrium was established. At equilibaum, the amount o: ==
Was 0.4 mol. Find the value of K,
‘Let the volume of the system be Vdm?. :
HCOOH + GHOHM = cH,cooc X
10 05 0 0
06 oF 04
110.4 moles of ester have formed, then ftom ts
from the balanced equstio
water must ao hae formed, and 4 moles ofeach ofthe eats
disappeared
H,COOC,Mal,0}
ICH;COOHIIC,H-OH)
ouve
Initial amount/met
Equilbrium amountimot
a
O.6VK0. 17}
927
‘a aus skin sade by cascnang 1 bomol
Aghc
FeSO, inate andmatog op tooS0Ge? ke con
‘Ag"aq) + Fe!(aq) <= FeP(aq) + Ag
At equiibrim, the concentration of Ag"
‘eaten petation of Ag*faq is found by titra
Find K. for the equilionum. abi
ove
pour fiche 4 the tol entropy change that sera at equlrnsm, not the ©
Tact total erry ofthe ayer sa maxims at equilbium ~ any cNarey>
pomtion woud result m 2 decrease mn total entropy
The relationship betowen these quantities 5 gree by ASn
gas constant. Snee R's 2 constant, an NCRAdE In ASy.9
aon constant K 5 wel (TIS apples to both equ
Hence, the total entropy Change not only indicates the spontarous 2
‘reaction but ao the extent to wh it takes place chow fart goes *
‘empleton). The ge the pasitve valve ofthe total entropy chang
Yala of K. tod 50 the further the equiisrum postion shits towor
Using entropy to explain the effect
temperature on an equilibrium
Both exothermic and endomeric veactions affect the ectrooy
8 Exotherersc reactions release evergy to the sur
i BS vrering « =4Ht
The comention for enthalpy changes is that AM 6. neq
Idole nga ate gue 8
i ca be wonton as ink (2) wx
awn industry
reactions are reversible. You should be able to explain how
Fequilbrum constant andthe ate constant ofthese reactions
reaction conditions, and to justify the choice of reaction
jn page 29 that the equilibrium constants K, and K. do vary with the
fe but do not change with either concentration or pressure (for gaseous:
ibrium and rate
speed up both forward and reverse reactions
ower the activation eneray see page 10).
~ © Gatats reduce the ume taken to estabish equilbnum
“& Gatalsis have no effect on the value ofthe equilibrium constants
Effect of temperature changes on
equilibrium and rate
Reversible reactions will be exothermic (AH negatwve) in one direction and
‘endothermic (AH positive) in the reverse direction. The temperature effects on yield
‘an be summarized as follows,
«in reaction where AH is positive, Krises with temperature increase, giving more of
the products
«© when AH is negative, K falls with temperature increase, ging more reactants,
‘increased temperature increases the rate constant k (see page 11), so the rate
“increases wath increasing temperature
the folowing equibna:
Nig) + 0:16) = 2NO(G) AH = +18540mol!
NYQ) + 3HAg) = 2NHla) AH = ~90KI mot’
What isthe effect ofinereasing the temperature on the postion of
- equilibrium?
Whats the effect of creasing the temperature on the sze of K,?
E ee
wy,
“Ralang the temperature favours endothermic processes. Reaction A shits
fo thesight, making more products, Reaction B shifts to the left, making
‘more reactants.
For reaction A there are now more products, 30 K, increases, For reaction
B there ate now more reactants, so K, decreases. 2
for reaction Ais likely to change more because the magnitude ofthe
‘AH term {the enthalpy 's large
A2 Chemisty Revision Guide Unit 4: General principles of chemistry | = Rates, equilibria and further organic chemistry
Effect of concentration and pressure
changes on equilibrium and rate
‘© Adding more reactants to an equilisium mixture accelerates the forward reaction
‘© As the amounts of products increase, the reverse reaction starts to speed up. & ne
Position of equilum is established but the value of K remains unchang}
‘©The pressure of a gas is proportional to its concentration. Changes of pressure also
do not affect the value of K
A change in pressure affects the position of equilibnum accortin
principle
+ Increasing the pressure of a gas means that there are more molecules in a
volume (equivalent to an increase in concentration) so they collide more freque
and the rate of a reaction increases
In the Haber synthesis for ammonia, use the changes in enth
{0 discuss the conditions used to obtain economic yields
Nig) + 34g) = 2NH,g) AH = 90K
‘> The forward reaction producing ammonia is exothermic, so low
temperatures wall favour high yields of ammonia
‘+ However, low temperatures will decrease the rate of the reaction
‘+ The forward reaction causes 3 decrease in entropy because the re
Product molecules than reactant molecules
‘= The forward reaction should be spontaneous only at jow ts
decrease in moles of gas, so there is a negative entropy ch,
Da
erry
[Lg emit nee because this lowers the number of gaseous molecsles and te
= Maintain very high pressures - energy Cost and strong conor:
We have no information at all about rate
fact te uncstaysedreacton has avery hgh actuation enecr a
f the triple bond in the N, molecule, which must first be broke
‘alah lowers the actuation energy, which accelerates the rete
The catalysts ton haps wath
surface area
4 Porous surface, This gives the
The conditions chosen for inc
‘acceptable reaction
n for industrial reactions are a comps
Fate k) and reasonable eqjuil The atom economy
Remember from AS Unit 1 that the efficiency of converting reactants into products can
bbe assessed using the atom economy
mass of atoms in the desved product | agq,
Total mass of atoms in reactants
‘The atom economy can be improved by.
‘© Developing an alternative more efficient synthesis ~ i find an alternative
reaction, such as finding a catalyst for a reaction with a better atom econmy, oF
replacing ehmination reactions with addition reaction.
Finding uses for any by-products ~e g in the cracking of decane to form two
Droducts, CigHoz — CoH: + CqHye, the atom economy is improved if commercial
Uses can be found for both products, not just the alkene. infact, octane is @ major
‘component of petrol
‘tom economy (26) =
= eqiriom constant?
§ goes up, how does the equltium constont chance
tenet 0 the yield ght rest Flom using a syrithess with &
yeconomy?
ton of ethandic acid, explain wh the Feaction.
Maas CHOH + CO = CH;COOH
“using catalysts of cobalt, rtiadium and chum, has 3 higher ston econciry
production of ethaioic acd from the oxidation of butane anc!
5 ‘which produces a wede range of products inciading ethanoi ec
* "acid, propanox ac and propanone.
A2. Chemisty Revision 6 Topics 3 and 4: Equilibria PP dict
rates and equilibrium checklist
By the end of this topic you should be able to
‘Revision spread [ Checkpoints
Fulvio mimures| Undead what we mean by dari equim
|
Game mporant reversble reactions | 48D
tied in manufacturing, such a5 the Haber process
| Tie Genin ona otk cuir [AGE and 43
| | constants, both for reactions and forthe
| dstrbuton of solutes between
| Use expresaons for Kn terms of equiiboum
| concetvations, and work out it urits
fees a ce fee mere
Gaseous equilbria | Use epresions for Kyi terms of equilbram
and K, | para pessures, and work out its units
|More on equilibrium | Use al data to work out equlioriom
[ethanoic acd
| [ie tak wtepy ond orton boat
| (ss
| constants | constants, eg: the reaction of ethan and
| | Uses costars pedct he poston | 459
[crow how temperature afecs the
| enanae
pectin. [as t
etc tod
eee Oo
|
QO
yO
1)
2 Comidr te equiv
NDlal=2NOa)-BH= +88KI mot
1 Write te expression fo the eultgm constant, K, forthe above ection
Pera
Avanos
Deel se sar bocs th wile yosmors Fue mr acs at ete ie:
‘6 1 Aneqaltsum mire catan moe rations of drogen tenovde 0, = 0.20, and of nitrogen dane, ND, = 0.80 To
esse ofthe mature 33 tm
Colbe ts temperate, stating ts uns.
‘NO;} = 060 X 11 atm = 088. a0m
AMDS=020%T1am=022em 1)
in lea?
Zain
Be mm
Yes fam swe ali pi bese inl pv! ea rine
Ree npre
Ht Caleta th otal pressure equine to ede th mo
AN,O4 = mote acon > stl pees oft yom» 01% Py
AN + AND = 1,s0 AND = 09 x P
Kiscorsam, 3820Im (1)
Sttsourg te exessien of
ay states ose ara er incre) ound thease 10
Irreasesbecaune ths an nator 000
The val of IND, P/pINatirceases
‘So he portal prescae of ND mut means 9 te oo
fight imabing moe NO). 10)
te i yo ace ad tou your answer (ih
iesere i tempertr lets he pitino Practice exam questions
1
Methanoic acid and ethanal react together to form the ester ethy! methanoate
HCOOC;H,, and water The reaction ts reversible and can be allowed to reach
equiibrum
HCOOHID + C,H,OHI) = HCOOCH.() +H.) BH = +451 mol
‘n an experiment, 3.00 mol methanovc acid, HCOOH, and 6 25mol ethancl
GH,OH, were mixed together. A small quantity of catalyst was added. The
mosture was left fr several days in a water bath to reach equilibrium at constar
temperature,
‘2 Copy and complete the table
‘Atstart of experiment | __3.00 625} 000 | om
At equilibrium 050 I
1b Wite an expression for the equilibrium constant, K., for the reaction
«€ Calaulate K- for the feaction at the temperature of the experiment
The total volume of the equilibrium mixture was 485 cr
State and explain whether or not K, for ths reaction has units. 1
@ I The temperature of this equilisium mixture is lowered. Explain the
effect of ths on the value of the equilibrium constant, and hence o
the yield of ethyl methanoate
li_A student added more catalyst to the mixture. State, giving 2
‘what would happen ta the composition of the equilibrium mixture 1
(Adapted from June 07 Unit test
For the reaction in the Haber process:
Nefq) + 3H,(q) == 2NH(q) AH ts negative forward
By keeping the pressure constant but raising the temperature, select
the following will increase as welt
‘A The time taken to establish equilibnum
BB The value of the equibium constant
C Both the forward and reverse reaction rates
D The partial pressure at equilibrium of ammonia
How can we change the value of the equilbrium constant for this re
Hi(Q) + I.(g) = 2g)
Select one from the folowing
A Adding a catalyst
B Adding some iodine
€ Raising the temperature
D Raising the total pressure of the system
Sich combination of conditions ges the most carbon dioxide in t
3 C2COJs) = C2019) + CONG)
Select one from the following,
‘A 900°C at 12.atm
8 100°C at tam
€ 450°C at 12atm
B 900°C at tatm
AY/'s postive forward (Tae
Aaa
for example concentrated sulfunc acid
‘such as citric acid in fruits
alkalis) giving a salt and water
to give salt, water and carbon dioxide
Asthenius developed a theory of electrolytic dissociation. It states that when certain
‘matenals dissolve in water, they immediately split up from molecules into ions
‘* Arthenius acids give hydrogen ions H” in aqueous solution
‘© Arthenius bases give hydroxide fons OH” in aqueous solution.
‘The theory could not be extended to include non-aqueous solvents such as liquid
Bronsted-Lowry theory
‘This theory was based on the movement of protons (equivalent to hydrogen ions. H")
{applied to a wider range of examples than previous theones. It said that a Bronsted
Loway:
‘+ acids a substance that donates protons
+ base i 2 substance that accepts protons
Conjugate acid-base pairs
The Brensted-Lowiy theory defines an acid-base pair 2 follows
‘to species that change into each other by gaining or losing a proton
+ ech 20d has 2 conjugate base
+ och bace has @ conjugate acid
For example, when hydrogen chloride gas dissolves in water, a solution of hydrachioric
208 formed
HCl) + H00) = Hy0"(aq) + Cag)
acd 1 base2 acd? baset
‘Acid 1 is transformed into base 1, its conjugate base. HCI donates @ proton to water,
k in wi asa base (base
leaving the conjugate base Cl(aq) In accepting a proton, water acts as a
2). is transformed by thes into ts own conjugate acid (aad 2), H,0*(2q)
AD Chemisty Revison Guite ‘Make clear in your answer wat
function the water is fling
‘Water canbe a proton donor ai or
repr base). Conusion over this
wills you mart,
Examples of Bransted-Lowry acids and bases
acids
‘© HNOs(aq) + H,00) = H,0°(aq) + NO;W(aq)
© CH;COOH(aq) + H,0() = H,0°aq) + CHCO,"(a@)
Bases:
‘© NH{aq) + H,O{) = NH,(aa)? + OH-aq)
‘© H5Q,-(eq) + H;0"(aq) = H,;S0,(aq) + H,0(0
‘completely ionized. These are strong acids, fully dissociated into ions
sodium hydroxide or potassium hydroxide are strong bases.
Some acids and bases are only partly dissociated into ions in aqueous solution
are called weak acids (e.g, ethancic acc) and weak bases (e 9.armmon
Ethanoic acid is only dissociated a few per cent (about 2%) in dilute aq
CHsCOOH(aq) + H,00
‘= Strong acids have weak conjugate bases.
Weak acids have strong conjugate bases PH and dissociation
“There are several mathematical relationships eating to the concentrations of hydrogen
“ions and! ions in aqueous solutions. Concentrations in mol dm. are written
_ as H"(eq)] and [OH “(aq)} respectively.
'¢ Use of a logarithmic scale allows easy comparison of concentrations that vary very
widely.
++ pH = —logylH(aqi. similarly POH = —log,clOH-aq)]
From the definition of the ionic product for water, k, (see below
‘= pH + pOH = 14 at 25°C, so knowing ether pH or pOH gies the other value
© PKy = —lodioKy
Make sue you can caleuat ig
from pH By reerangenen,
(Hal = antlon pH) You fra
‘his by using the 10 furetion on your
‘lela
lonization of water Nese aa
‘Water dissociates weakly into ions:
1,04) = H*(aq) + OH-(aq)
A equilibrium, we can write en expression forthe equilibrium constant
_ (OH (aailt(aqi
LOW]
‘Since the extent of dissociation 1s very small, {H,0())] varies very little indeed and it is
Useful to treat this as a constant, and write an expression called the ionic product for
water Ky:
K
K, = {OH-Caa)itt*(aq)], this has units mol? dm-*
Note that the ionzation of waters endothermic (the equilnum shifts tothe
fight at higher temperatures), so K, depends on temperature At 25°C.
Ky =1.0X 10°" mol dm-*
Taking log,» of both sides ita hata ruta sion fas
pk, = pit + poH 1H te denept
K, = 1.0 x 10° mo’ dm~* at 25°C \ ei
fence pH + pOH = 14 at 25°C
We can use the value of K, to calculate either the pH or the GOH ofa solution.
oem
Find the pH of a 0.05 mol dm” solution of the strong base sodium hydroxide,
©) Ke = {HP leq)OH(aq)l = 1.0 x 10°" mol? dm-*at 25°C
~ {0H -(aq)] = 0.05 mol dm-* because it's fully dissociated into ions.
Therefore, 1.0 x 10°" mol?dm”* = |H*(aq}] x 0.05 moldm=?
© tH @q) = 2 « 10° mot dm?
“© p= logiel2 x 10-') = 12.7
Dilution effects
# Strong acids are already fully dissociated into ions in dilute aqueous solutions, so
[H"(aq)} = acid, the acid concentration in mol dm
‘= Diluting a strong acid by a factor of 10 raises the pH by 1 unit
‘© For an acid lke hydrochloric acid
jam
'sDiluting 2 weak acid is different; i increases the degree of dissociation into ions
(Gee below),
2 Chemisty Re i
Cara w
4) + Mopoteni tts ie one rept
12 hydrogen atom ~ for example HC
“| CH,COOH and HNO;, Sulfunc os
6
‘
2
See
coef xml ok thal ‘adding acid to base.
{2d io 25H" 3 1 el oad
section of the pH curve, where ¢
changes most rapidly
‘# There 5 10 sharp change of pi
‘acid-weak base trations, maki
Note that: es
‘© only the titrations of strong acid
bases give end-points with
© neutrakzation of a weak acid o:
owes the end-point above 0°
‘on 001 ed on * at me
ded to 25cm 1 Mol dm Yd eed 0 259 1 red ces eee
Vanden of pH during erations
Yeu tout be abe seth eon
| cues tr a geen at-bat ttn
Th start part ne gH came
calouates ham te sents ad he
anaes of be ace or bose beg,
sad The ec pot pa te
rape ote weve! part bed the
(ee gt a8 0 abet the ar
Ls be Pring Pe
ser atest 9 91 tage eat
a seam see
Indicators
Colour-change indicators are weak organic acids o bases:
Choose 3 suitable eccator tor the folinwing trator, ant expia~
2 ethanok: sod and sodhum Pucronde, s
1b inydrochiore acd and potassium Mycraside
© ethan aod and ammarea sokuton
12 Yea acd ster bane: priced Oa the pure
strong 9 8 the er geet srs
(© Stor ack storg bine, vero eection oF he Beatin cave“:
we ang: ay chor wh ee
¢ Wek 40d — ytiak asin m0 clear DM he ne
Feet Stale rina By the end of this topic you should be able to
Revision spread | Checkpoints.
‘Acids and bases | Understand the Arrhenius and the 47a
Bronsted-Lowry theories
‘nderstand conjugate aad~base pars in terms of | 4 7b and c
proton transfer
now that weak ads and bases are onlysightly | 47e
dissociated in aqueous solution
Saks tunte ers frau atone “| 37
Understand how buffer solutions maintain pH and | 4 7k
{culate the pH of buffer solutions
[Use tiation curves fo relate K, and pH at hal
1 Tet
low sociation Setup when ethenic ai Sissoltes in water
Ohta) = Oa
‘a Wonte the expression tar’ .
scnation constant, Kfar ethanoic cis
= (CREO, IM VICH.COOH a autre’)
The mesa aks for K, fr eho acd
_} Geen = 18% 10"?nol dir | old eben i, cae he pi a
Ia weak ci nase that hie itl disci
{OCD TH ACH comm
=X 0a on
He imal} 24)
Wiio
m1
iw
use Be abet DF tan on orion conan if
‘Tyee wnte hd geen equation yea wi ose mars ven yd wre the geri ca»
eas ton, $0 tat the fina concentration, (CH/COOH) 'S approAMAREy 1. mo! an
‘pH and dissociation | Expian the meaning of pH, K,. OK. KK. 476 i
Constants =
‘Wiite expressions forthe equilbrium constants K, | 47e and f ol
and K, and deduce their units e
‘Use logs and antlogs to earry out pH caleulations | 47d and f ol
fora stiong acd and a weak acid, cluding after
{ diution
| Understand the Feationship between K, and pH [47a andh 1
| Horweak acids, and discuss the assumptions in the ‘|
he
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