Recapitulation : kinetics

d(reaction product) d(reagent)

v= = -
dt dt
k (not K) rate constant
Order (global order) of the reaction : first order, second order, …. v = k [A]x[B]y

First order : ln (a-x) = ln a – kt with t = time

Slope -k

Second order 1
1
= + kt
a-x a

Half life t1/2 (for first order t1/2 = ln2/k)

 Recapitulation : kinetics
Temperature dependance of k Arrhenius equation: k = A e-Ea/RT

Rate constant k always goes up when T increases (Ea is positive)

Ea 1 1
From logaritmic equation follows k1 = - -
ln T1 T2
for two temperatures T1 and T2 k2 R

Collision theory v = R x f x p with R conc. dependent, f (energy factor) like e-Ea/RT

and p (steric factor) equal to A

Transition state : energy maximum

on reaction coordinate (= reaction progress)
 Recapitulation : kinetics
Elementary reactions, reaction mechanism
Rate determining step

The figure on the right : two elementary reactions

Global reaction : from reactant to product
Rate determining : step 2 (largest Ea)

Chain reactions (via unstable intermediates), explosions

Catalysis : homogeneous, heterogeneous

Lower Ea
 Recapitulation : kinetics

1. Discuss the factors that determine the reaction rate according to the collision
theory

See theory = R x f x p

with

R = collision frequency, proportional to [X][Y] ;

f = energetic factor = e-Ea/RT 0 < f < 1 (fraction of collisions with sufficient kinetic
energy)

and p = steric factor 0 < p < 1 (p = fraction of collisions with the right orientation)
 Recapitulation : kinetics

2. Discuss the following phrases: a) The Arrhenius constant A agrees with the
value that k would have if all collusions were sufficiently energetic. b) There is a
relation between the Arrhenius constant and the orientation of the reagents during a
collusion c) There is a relation between Arrhenius constant and the entropy of
activation

a) If all collusions are sufficiently energetic it means –Ea/RT = 0

so k = A e-Ea/RT becomes A
b) Indeed, because the orientation is the steric factor p, and that equals A
c) Indeed, for the transition state
k ~ K‡ (a) and K‡ = e-ΔG‡/RT ; k ~ eΔS‡/R e-ΔH‡/RT = eΔS‡/R e-Ea/RT (ΔH‡ = Ea)
 Recapitulation : kinetics
3. The bromate ion and the bromide ion react in acid environment to dibromine.
The initial rate of formation of dibromine (l) is measured in function of the initial
concentrations (in mol/L) of the bromate ions, the bromide ions and the protons :
[BrO3-] [Br-] [H+] v (mol/L.s)
0.10 0.10 0.10 8.0 10-4
0.20 0.10 0.10 1.6 10-3
0.20 0.20 0.10 3.2 10-3
0.10 0.10 0.20 3.2 10-3
Determine the format of the rate equation.
Answer : v = k[BrO3-][Br][H+]2
 Recapitulation : kinetics
4. Aspirin is metabolized (broken down) in the body by a first order reaction. The
half life is three hours. Calculate how many mg aspirin remains five hours after
taking a tablet containing 200mg aspirin (assuming everything is taken up).

t1/2 = ln2/k = 3 h so k = (ln2)/3

after 5 h: ln(a-x) = lna –5k = lna - (5/3).(ln2)

or a-x/a = 2-5/3 = 0.315 = (1-degree of conversion) = the fraction remaining

(1-degree of conversion) x amount at the start = 0.315 x 200 mg = 63 mg

 Recapitulation : kinetics

Exercise
10% of a sample reacts in 45s. If the reaction follows first order kinetics, how
long would it take for half the sample to react?

First order answers to the equation ln(a-x) = lna-kt

For t = 45s the (a-x) = 0.9a (10 % has reacted) so we can calculate k
ln(0.9a) = lna + ln(0.9) = lna –kt with ln (0.9) = -0.1054 and t = 45s
It follows that k = 2.34 10-3 s-1

t1/2 = ln2/k = 0.693/(2.34 10-3) = 296s

 Recapitulation : kinetics

Dinitrogen pentaoxide (N2O5) is allowed to

decompose (assume first order kinetics) in
a closed vessel into nitrogen dioxide and
dioxygen. In the figure below, the logarithm
of the concentration of dinitrogen
pentaoxide is plotted in function of the time
(in s) at two temperatures : 35°C and 45°C.

a) Which temperature can be assigned to

which line?
b) Calculate the activation energy.
 Recapitulation : kinetics
k is always larger for larger T, so more conversion at higher temperature, the
lower line is the one at higher temperature
we have to use the equation ln(a-x) = lna-kt and

With T1 = 308 K and T2 = 318 K, R = 8.31, we still need k1 and k2

Start ln(a) = -2.3 after 1500s (at 308K) ln(a-x) = -2.5 thus 0.2 = 1500k 1 and k1 =
1.33 10-4 s-1, for k2 same calculation gives k2 = 5 10-4 s-1
Apply to formula above and derive Ea : 107.8 kJ/mol
 Recapitulation : equilibrium
Chapter 13 : Chemical equilibrium, concepts
Equilibrium state, dynamic equilibrium, degree of conversion of a reaction
Equilibrium constant K : equation, reactions in gas phase, Kc and Kp
Heterogeneous equilibria
Calculating K, equilibrium concentrations
Relations between K’s, combinations
Thermodynamic approach equilibrium : ΔG° = -RTlnK
Kinetic approach equilibrium K = ratio k (forward) /k (return)
Shifting the equilibrium : influence T, conc., pressure
 Recapitulation : equilibrium
general form for reaction rR + sS xX + yY

[X]x[Y]y [pX]x[pY]y [X]x(RT)x[Y]y(RT)y

Kc = Kp = Kp = = Kc(RT)n
[R]r[S]s r
[pR] [pS] s [R]r[RT)r[S]s(RT)s

Kp is used for reactions with gases

Calculations of K from concentrations (or vice versa)

Relations between reactions : for instance

K(3) = K1.K2 if reaction 3 = reaction 1 + reaction 2
K(3) = K1/K2 if reaction 3 = reaction 1- reaction 2
K(3) = (K1)2/K2 if reaction 3 = 2x reaction 1 – reaction 2
 Recapitulation : equilibrium

combining reactions

AgCl(s) Ag+ + Cl-

PbCl2(s) Pb2+ + 2Cl-
PbCl2(s) + 2Ag+ 2 AgCl(s) + Pb2+

reaction 3 = reaction 2 – 2x (reaction 1)

thus eliminating chloride-anion

 Recapitulation : equilibrium
PbCl2(s) Pb2+ + 2Cl- reaction 2
-2AgCl(s) -2Ag+ - 2 Cl- -2x (reaction1)

PbCl2(s) - 2 AgCl(s) Pb2+ -2Ag+

PbCl2(s) + 2Ag+ Pb2+ + 2 AgCl(s)

reaction 3

Only the same entities (molecules, ions) can be added or substracted (not CO2
–CO = C)
negative coeffients = bring to the other side of the equation
 Recapitulation : equilibrium
For the free energy:
ΔG(3) = ΔG(2) - 2ΔG(1)

so –RTlnK(3) = -RTlnKsp(PbCl2) + 2RTlnKsp(AgCl) (divide by –RT)

or lnK(3) = lnKsp(PbCl2) - 2lnKsp(AgCl) = lnKsp(PbCl2) - ln(Ksp(AgCl))2

Ksp(PbCl2) [Pb2+]
K(3) = =
(Ksp(AgCl))2 [Ag+]2
 Recapitulation : equilibrium
Kinetics, thermodynamics and K
graph of free energy in function of reaction coordinate
activation energy Ea determines k (rate constant) with Arrhenius formula : k = A.e-Ea/RT since
Ea is always positive, k always increases when T increases = kinetics

difference in free energy between reagents and products ΔG

determines K (equilibrium constant) according to formula
ΔG = -RTln K of K = e-ΔG/RT
ΔG can be positive (endergonix) or negative (exergonic)
when the temperature rises K may increase or decrease = thermodynamics
 Recapitulation : equilibrium
Kinetics, thermodynamics and equilibria
graph of free energy in function of reaction coordinate

k = A. e -Ea/RT

k = A. e -Ea/RT

DG = -RTlnK = Ea - Ea

k
K=
k
 Recapitulation : equilibrium
Thermodynamic equilibrium constant ΔG° = -RTlnK

Principle of le Châtelier : when T, conc. or pressure of a system in equilibrium

change, the equilibrium shifts in that direction in which the change made is reduced.
S
Temperature dependence of K R
lnK

lnK -H
r.c. =
R
-H
S r.c. =
R

-G° -H° S° 1/T (K)

R
1/T (K)
RT R
K=e RT = e e endothermic exothermic

H° S° K1 H° 1 1

lnK = - + ln = - -
RT R K2 R T1 T2
 Recapitulation : equilibrium
1. The acetate ion partially transforms in water to acetic acid :
CH3COO -
+ H2O CH3COOH + OH-

In a 0.10 molar solution of sodium acetate the degree of conversion of the acetate
ion at 25°C is 7.5 x 10-5. Calculate the value of the equilibrium constant.

For this reaction we have the conversion formula K = α2C/1-α so after

simplification of 1- α to 1 (α is very small)

K = α2C = (7.5 (10-5))2 (0.1) = 5.6 10-10

 Recapitulation : equilibrium
2. Calculate the values of the equilibrium constants Kp and KC at 25°C and at 1000°C of the reactions :
a) 2NO(g) + O2 (g) 2NO2 (g)

b) CaCO3 (s) CaO(s) + CO2 (g)

Method; calculate ΔH°, ΔS° of the reaction table 4), and then ΔG = ΔH°-TΔS°
For reactions with gases ΔG = -RTlnKp
Convert Kp into Kc via Kp = Kc(RT)Δn First reaction Δn = -1, second Δn = +1

a) ΔH° = -114.3 kJ/mol, ΔS° = -146.5 J/K.mol ; at 25°C ΔG = -70.3 kJ/mol; Kp = 2.15 1012;
Kc = KpxRT = 5.25 1013; at 1000°C ΔG = +72.0 kJ/mol, Kp = 1.10 10-3 ; Kc = KpxRT = 0.014

b) ΔH° = +178.3 kJ/mol, ΔS° = 160.5 J/K.mol; at 25°C ΔG = +130.5 kJ/mol and Kp = 1.29 10-23;
Kc = Kp/RT = 5.28 10-23 ; at 1000°C ΔG = -26.0 kJ/mol; Kp = 11.7 ; Kc = Kp/RT = 0.112
 Recapitulation : equilibrium
3. In a degassed reactor, methane and water vapor are mixed. A partial conversion
occurs to carbon monoxide and dihydrogen :
a) Calculate at which temperature the value of the equilibrium constant Kp equals 1.0
b) Discuss the influence of an increase of the temperature at constant pressure on the
molar fraction of dihydrogen
c) discuss the influence of an increase of the pressure at constant temperature on the
molar fraction of dihydrogen.
 Recapitulation : equilibrium
Reaction : CH4 (g) + H2O (g) → CO(g) + 3H2 (g) (equilibrium)
ΔG° = -RTlnKp en Kp = 1 so ΔG° = 0 = ΔH°-TΔS°
It follows that ΔH° = TΔS°
ΔH° and ΔS° can be calculated (resp. +206.1 kJ/mol and +218. 8 J/K. mol) using
the book of tables (table 4), this allows to determine T (in K) as
T = ΔH°/ΔS° = 942K
b) when T increases, TΔS° > ΔH° so negative ΔG° , reaction to the right (products),
molar fraction of hydrogen increases
c) amount of mole gas increases after reaction : equilibrium shifts to the left (less
mole gas) when increasing the pressure (Le Chatelier)
 Recapitulation : equilibrium

4. Discuss the conditions needed to have a reaction with gaseous reagents

and gaseous products so that
a)The value of Kp increases with increasing temperature
b)The value of ΔG° increases with increasing temperature
c)The value of k increases with increasing temperature
d)The conversion of one of the reagents increases with increasing pressure
 Recapitulation : equilibrium
1) Value of Kp increases with increasing temperature :
ΔG° = -RTlnKp so Kp = e-ΔG°/RT and ΔG° = ΔH°-TΔS° so Kp = e-ΔH°/RT eΔS°/R
ΔH° has to be positive (endothermic reaction) for increase of Kp with rising T
2) Value of ΔG° increases with increasing temperature: see ΔG° = ΔH°-TΔS° this
requires ΔS° to be negative, so less disorder = less gas particles
3) Value of k increases with increasing temperature : no conditions, this is always the
case since Ea is positive!
4) The conversion of one of the reagents increases with increasing pressure :
Le Chatelier : after increasing the pressure the reaction shifts in the direction where
the amount of gas particles decreases, so the amount of gas molecules must
decrease to shift the reaction to the right.
 Recapitulation : equilibrium
Exercise 0,40 mol pure sulfur trioxide is heated in a closed vessel and decomposes
partially in sulfur dioxide and dioxygen. At 1000 K 0,10 mole dioxygen has been
formed, all substances are gaseous and the volume of the gas mixture is 27 L.
a) Calculate the value of the equilibrium constant Kc at 1000 K
b) Calculate the value of the equilibrium constant Kp at 1000 K
c) Calculate the degree of dissociation of SO3

Answer : equation 2SO3 2SO2 + O2 For 0.1 mole oxygen to be present, 0.2
mole SO2 is required to form, this means that 0.2 mole SO3 remains. Derive equation
for K and apply equilibrium concentrations, Kc = 0.1/27 = 3.7 10-3
b) Answer Kp = Kc.RT = 0.30 (for T = 1000 and R = 0.082)
c) Half of the SO3 is dissociated, 0.5 (or 50 %)
 Recapitulation : equilibrium
Solid NaHCO3 decomposes on heating to solid Na2CO3, carbon dioxide and
water vapor. In a closed system, an equilibrium state is reached.
Discuss the influence of an increase of the volume at constant temperature on
a) the value of the equilibrium constant and
b) the degree of conversion of NaHCO3.
Discuss the influence of an increase of the temperature at constant volume on
c) the value of the equilibrium constant
At constant V and T, d) what happens if Na2CO3 is added ?

a) No influence, K remains constant as long as T is constant

b) Higher V is lower P, more gas formed, more NaHCO3 converted
c) reaction endothermic (+136 kJ, calculation) : Kp is larger when T increases
d) Nothing, solids have constant concentration