Thermodynamics and Chemistry of Solutions/ chapter I 1st common core: NLS

Chapter I: Chemical kinetics

1- Object of kinetics
The study of thermodynamics informs us about the possibility (or impossibility) of a particular
reaction to occur at a given temperature.
The object of chemical kinetics is the study of the evolution over time of a chemical reaction
thermodynamically possible.
Chemical reactions can be divided in two categories:
- Those which are instantaneous: The reagents are consumed very quickly (acid-base,
precipitation reaction…….).
- Those whose evolution is slow: The reagents are only consumed after a certain time (of the
order of a second, m, h….) (Water synthesis, esterification reaction …….).
2- Kinetic factors
These are the parameters on which the law of evolution depends of the reaction system;
- Concentration C (Rate equation: r= dC/dt………),

- Temperature T (Arrhenius equation ),

- catalyst…………
3- Concepts of reaction rate
A reaction is not an instantaneous phenomenon. It is a process that takes place over time, and
which has duration. At any moment during its course, reagents molecules disappear and product
molecules are formed.
3-1- Average rate - instantaneous rate
To study the evolution of a chemical system over time, it is necessary to be able to measure the
quantity of product P formed or unconsumed reagent R during a given time interval:
- If the quantity of P produced is n1 at time t1 and n (mol)
P
n2 at time t2, the average rate ravg defined by:
n0 P
ravg = n2 –n1 / t2 – t1
T2
n2
The instantaneous rate rinst, at a moment t, is equal
When (t2 – t1) →0: T1
n1
rinst = dn / dt = lim (n2 – n1/ t2 – t1)
∆t→0 R
t(s)
t1 t2
rinst and ravg expressed in mol/s or mol/min, h etc….
Fig-1: The variation as a function of “t” of the quantity of a
product P formed or the unconsumed quantity of a reagent R

1
Thermodynamics and Chemistry of Solutions/ chapter I 1st common core: NLS

The instantaneous rats at times t1 and t2 are defined respectively by the slope of the two
tangents to the curve T1 and T2.
3-2- Rate of variation of the concentration of a chemical species
The rate of a reaction is defined as the variation in concentration of reactants or products per
unit of time. The mathematical expression of the rate equation is often given by:
r = dC / dt = d[…] / dt
We have the chemical reaction: a A + b B c C + d D.
The reactants are the substances of the first member A and B, the products are the substances
C and D. The quantities of the reactants decrease over time, on the contrary for the products.
a, b, c and d are the stoichiometric coefficients.
The stoichiometry of the reaction shows that if "a" mol of A and "b" mol of B disappear, it
appears "c" mol of C and "d" mol of D, therefore the concentration variation is proportional to
the stoichiometric coefficient.
- We define the rate of a reaction by the variation of molar concentration in (mol/l) as a function
of “t”.
r = -d[A] / a dt = -d[B] /b dt = d [C] / c dt = d [D]/d dt
so: r = rA / a = rB /b = rC / c = rD /d
with: rA = -d[A] / dt, rB = -d[B] /dt, rC = d[C] / dt and rD = d[D]/ dt
We can say that rA and rB are transformation rates and rC and rD, formation rates.
Example:
1- F2O2 F2 + O2
The reactant disappears at the same rate as the products are formed
r = -d [F2O2] / dt = d [F2] / dt = d [O2] / dt
2- 2NO2 2 NO + O2
r = - d [NO2]/ 2dt = d [NO] /2dt = d [O2] /dt
r NO2 = r NO = 2 r O2
3- C2H2 + 2H2 C2H6
Dihydrogen is consumed twice more rapidly than acetylene:
r = d [C2H6] / dt = -d [C2H2] / dt = -d [H2] /2 dt
In the case where the reaction mixture is gaseous or consists of a single perfectly stirred liquid
phase: We speak of homogeneous reactions.
4- Formal kinetics (the rate law and the order of a reaction)
The object of this part is the mathematical study of the relationships between concentrations
and time t.

2
Thermodynamics and Chemistry of Solutions/ chapter I 1st common core: NLS

Experience shows that we can often represent the rate “r” by the expression:
r = K [A]α [B]β……….. (*)
Depending on the Rx: aA + bB+ …… cC + dD
The relation (*) called the rate law which reflects the decrease in rate with the concentration
of the reactants. Sometimes we observe an influence of the concentration of the products on the
reaction rate (r = K [A]α [B]β[C]γ ………..).
K: rate constant (depends on temperature, characteristic of each reaction).
-α, β etc…: Partial orders of the reaction with respect to each reactant A, B, etc…. They can be
whole numbers (integers) or fractional, positive, null or negative.
α + β + …………= n, is called the order of the reaction (overall).
Remark
Consider the reaction: A + B C
r = -d [A] / dt = - d [B] / dt = K [A]α [B]β
We assume, for simplicity that at zero time: [A]0 = [B]0 and at any time t: [A] = [B],
Since n= α+β so: r = K [A]α+β = K [A]n
4-1- Zeroth order reaction (n=0)
Let the reaction be: A B A

r = -d[A]/dt = d[B]/dt
A tgo= - K
r = K[A]n = K[A]0 = K “r” is constant 0

o
by separating the variables, it comes: A =f(t)
[A] t

d[A] = -K dt → [A]0∫ d[A] = -K 0∫ dt t

[A] = [A]0 - Kt
[A]0: initial concentration of A
Half-life of the reaction
Is the time at which half of the reagent has disappeared : t = T½ → [A] = [A]0 /2
[A]0 /2 = [A]0 – K T½ → T½ = [A]0 / 2K
K expressed in mol.l-1.S-1 and T½ is proportional to [A]0, we can determine T graphically

4-2- First order reaction (n=1) ln[A]

log A
0
r = K [A]1 = -d[A]/dt
log 0A
ln[A]
d [A] / [A] = -K dt 0

[A] t
o tgo= - K

[A]0∫ d[A]/ [A] = -K 0∫ dt

log Af(t)=f(t)
ln[A]=
ln [A] – ln [A]0 = -Kt → t
0

3
Thermodynamics and Chemistry of Solutions/ chapter I 1st common core: NLS

Half-life of the reaction A

t = T½ → [A] = [A]0 /2
[A]0 / 2 = [A]0 e-KT½ → T½ = ln 2 / K A
0 A =f(t)
-1
K expressed in S and T½ is independent of [A]0,
it is a characteristic property of first order kinetics. A /2
0

t
4-3- Second order reaction (n= 2 ) T1/2
1/ A
r = -d [A] / dt = K [A]2 → -d [A] / [A]2 = Kdt
[A] t
[A]0 ∫ -d [A] / [A]2 = K 0∫ dt tgo= K
o
1/[A] =1/[A]0 + Kt →[A] = [A0] / (1 + [A]0 Kt) 1/ A
0

1/ A =f(t)
t
Half-life of the reaction A

T½ = 1/ K [A]0
A A
K expressed in mol-1.l.S-1 0 A 0
=1+ A Kt
0
T½ is inversely proportional to [A]0 and
A
0
/2
T½ [A]0 =1/K is a constant
t
T1/2
4-4- General case, nth order reaction
A Rx of the nth order with respect to one of the reactants “A” obeys the rate law:
r = -d [A] /dt = K [A]n → d[A] / [A]n = K dt
[A]t

[A]0∫ [A]-n d [A] = K 0∫ dt → (-1/1-n).([A]1-n - [A]01-n) = Kt

(1/n-1).([A]1-n - [A]01-n) = Kt (with n ≠ 1)
(2𝑛−1 −1) 1
Kt and T =
1/2 (𝑛−1)K [𝐴]0𝑛−1

K expressed in mol1-n. ln-1. S-1 and T½ is inversely proportional to [A]0 and

T½ [A]0n-1 = (2n -1 –1)/K(n-1) = const

5- Experimental kinetics: Determination of the order

5-1- Initial rates method (by determination of the partial orders)

his can be used to estimate the order of reaction of each reactant. For example, the initial rate
can be measured in a series of experiments at different initial concentrations of reactant A with
all other concentrations [B], [C]……… kept constant.

4
Thermodynamics and Chemistry of Solutions/ chapter I 1st common core: NLS

The value of α can be determined by inspecting the rate at different values of [A]. if we know
the initial rates at two different concentration of A: (r0)1 = K [A0]1α [B0]β and
(r0)2 = K [A0]2α[B0]β
(r0)1 [A0]1 α (r0)1 [A0]1
= ([A0]2) → 𝑙𝑛 (r0)2 = α ln ([A0]2 )
(r0)2

5-2- Graphical method

The graphical method involves graphically representing experimental data, such as the
concentration of a chemical species as a function of time, to analyze the kinetics of a reaction.
We are looking for the function of [A] which varies linearly with time.

Order of the reaction Linear graphs rate constant K

Zero order [A] = [A]0 – Kt [A] − [A]
K= 0
t
First order ln [A] = ln [A]0 – Kt 𝑙𝑛[A] − ln[A]
K= 0
t
Second order 1/[A] = 1/[A]0 + Kt 1/[A] − 1/[A]
K= 0
t
: : :

nth order 1/[A]n-1 = 1/[A]0n-1 + (n-1) Kt 1/[A]𝑛−1 − 1/[A]𝑛−1

0
K=
(n − 1)t

5-3- Half-life method

Depends on the relationship between the half-life (T½) and the initial concentration of reactant
A ([A]0).
[A]0 …………
T ½ …………

- Zero order: T½ = [A]0 / 2K and T½ is proportional to [A]0

- First order: T ½ = ln 2 / K and and T½ is independent of [A]0
- Second order: T½ = 1/ K [A]0 …..T½ is inversely proportional to [A]0 and T½ [A]0 = const

(2𝑛−1 −1) 1
- nth order (n ≥ 3): T = ………T½ is inversely proportional to [A]0 and
1/2 (𝑛−1)K [𝐴]0𝑛−1
T½ [A]0n-1 = const

5
Thermodynamics and Chemistry of Solutions/ chapter I 1st common core: NLS

5-4- Van’t Hoff differential method

r = K [A]n → we can also write: ln r = ln K + n ln [A]

By plotting the graph (1): ln r = f (ln [A]), the order “n” is the slope of this line.
The graphic determination of the rates r1, r2, .... rn at times t1, t2, .....tn is done by the slope of the
tangent to curve (2): [A] = f (t) (instantaneous rates).

log v A
Ln r
(1) (2)

Lnlog
r2 v tgo = n
Lnlog
2
r1 v1
o
A1 A

t
Ln[A]
log A t
log A log A t1
ln[A]1 1 ln[A]2 2

graph (1) graph (2)