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dc P dcP
Rate of reaction = - or, rate of reaction = +
dt dt
Where dCR and dCP are change in concentration of reacrants and products,
respectively. –ve sign suggests decrease in the concentration of reactants while
+ve sign suggests increase in the concentration pf products with time, as shown
by the graph. concentration
Let us suppose a general reaction : aA + bB → cC + dD
where, a , b, c and d are the no. of moles of A, B, C and D respectively
thus, at any instant :
reactants
time
dC A 1 dC A
rate of disappearance of A = - ∴ rate of reaction = -
dt a dt
dCB 1 dC B
rate of disappearance of B = - ∴ rate of reaction = -
dt b dt
dC C 1 dC C
rate of disappearance of C = + ∴ rate of reaction = +
dt C dt
dC D 1 dC D
rate of disappearance of D = + ∴ rate of reaction = +
dt d dt
1 dC A 1 dC B 1 dC C 1 dC D
So, - = - = + = +
a dt b dt C dt d dt
K t+10 K t+10
= 2 to 3, is called temperature coefficient
Kt Kt
∆t
In general, rt =r0 x ............. (1)
10
time time
o o
6. A catalyst, particularly enzymes catalyst is highly specific in nature.
7. There is an optimum temperature for a catalysts at which its efficiency is maximum.
TYPE OF CATALYSIS :
There are two types of catalysis
(1) Homogeneous Catalysis
(2) Heterogenous Catalysis
1. Homogeneous Catalysis: In homogeneous Catalysis reactants, products and catalyst, all exist in the
same phase as homogeneous mixture. e.g.,
2SO + O No 2SO
2 2 3
2. Heterogeneous Catalysis : When catalyst and reactant from two phases, it is called heterogenous
catalysis. e.g.,
MnO2 (S)
KClO3 (S) KCl (S) + O2 (g)
Catalytic Promoters : A substance which itself is not a catalyst but when present with catalyst increases
the rate of reaction is called catalytic promotor.
N2 + 3H2 2NH3 (slow)
Mo
N2 + 3H2 2NH3 (slow)
Fe
N2 + 3H2 2NH3 (fast)
Fe
N2 + 3H2 Mo 2NH3 (more fast)
Thus, in the above example, Fe is catalyst while Mo is catalytic promoter.
Catalytic Position :
A substance which destroys the catalytic activity of a catalyst is called catalytic poison. e.g., The rate of
formation of SO3, in contact process is slowed down considerably if some arsenic compounds are present
even in traces. Hence arsenic compounds act as poison for platinum catalyst. A catalytic poison is preferably
cover the active surface of the catalyst.
A
k2
C
the overall reaction is
A B+C
k
then k = k1 + k2.
CE
Kc=
C A × CB
dx dx
∝ (a - x)1 = k(a - x)
dt dt
PHYSICAL CHEMISTRY Page No.: 6 By: Shailendra Kumar
Where, k = constant, called rate constant, or velocity constant or specific reaction rate constant. It is a
constant for a particular reaction at a given temperature.
dx x dx t
⇒ = kdt ⇒∫ = k ∫ dt
a-x oa-x o
2.303 a
k= log
t a-x
This is called first order equation.
It initial concentration = a = C0 or N0 and concentration after time t = (a – x) = C = N
∴ First order equation can be written as
C = Coe–kt or N = Noe–kt
Thus concentration of the reactant A varies exponentially with time (See graph). These equation is called
Wilhemy’s equation.
Also first equation is different from
2.303 a – x2
k= log10
t2 – t1 a – x1
Where (a – x1) and (a – x2) are the concentration of the reactant at time t1 and t2 respectively.
(1) Unit of K :
dx
For the order reaction, = k(a – x)n
dt
dx 1 [conc]
∴k= n × = n
(a-x) dt [Conc] [time
∴ k = [Conc]1-n [time]–1
∴ If Conc = mole litre–1
∴ k = mole1-n litren-1 time–1
For Zero order reaction, n = o, k = mole litre–1 time–1
First order reaction, n = 1, k = time–1
Second order reaction, n = 2, k = mole–1 litre time1
Thus, we find that, only for 1st order reaction, value of k is independent of the unit of concentration.
(2) Rate of reaction :
Rate of reaction is a constant and is equal to velocity constant.
dx
= k(a – x)o = k
dt
= k(a – x)
Rate of 2nd order reaction is directly proportional to square of conc. of reactant. e.g.
dx
= k(a – x)2
dt
dx dx dx
dt dt dt
Zero order reaction First order reaction Second order
reaction
o (a – x) o (a – x) o (a – x)
Thus, we find that only a Zero order reaction can be completed.
(3) Time required to complete a half of reaction: (half-life)
For Zero order reaction :t1/2 = a/2 i.e. t1/2 ∝ a.
For 1st order reaction : t1/2 = 0.693/k i.e. t1/2 = constant
Half life of first order reaction is
T1/2 = T50 = ln2/k = 0.693/k
Here T1/2 can be denoted by T50 i.e. time required for 50% completion of reaction, then
dx
! At t = T50 , x = a/2, (a – x) = a/2
dt
T50 = 1 × t50
! At t = T75, = x = 3/4a, (a – x) = a/4 [where T75 is the time required for 75% completion of
reaction]
Hence T75 = 2 × T50
! Also T87.5 = 3 × t50
:
T99.9 ≈ 10 × T50.
Thus completion of 50% reaction and each subsequent 50%
(i.e. 75%, 87.5%, 63.75% ..........99.9%) completion takes equal time.
1 1
For 2nd order reaction, t1/2 = i.e. t1/2 ∝
ak a
t1/2 t1/2 t1/2
2.303 a kt
k= log ⇒ = loga – log (a – x) log (a – x)
t a–x 2.303 A
kt
kt slope =
⇒ log (a – x) = – + log a 2.303
2.303 OA = log a
o t
kt
So, the slope = – and intercept = log a.
2.303
(5) Average life of 1st order reaction :
1/k is known as average life Tav of first order reaction
1 T
50
T = = = 1.443 T
av k 0.693 50
2NO2
When the reaction is carried out in the solution, N2O4 and NO2 remain in the solution and the volume of
oxygen gas collected is noted at different intervals of time. It is obvious that
Volume of oxygen gas Amount of N2O5
∝
collected at any time (Vt) decomposed (X)
i.e. x ∝ Vt
Volume of oxygen gas Amount
Collected at infinite time of N2O5
∝
time (V∞) (Which is done by initially
heating the reaction vessel) taken (a)
i.e. x ∝ V∞
Substituting these values in the first order equation viz.
2.303 a
k= log
t a–x
The constancy in the value of K proves the reaction to be the first order.
(ii) Hydrolysis of Ethyl acetate :
CH3COOC2H5 + H2O H+ CH3COOH + C2H5OH
In the reaction, acetic acid is one of the products, the amount of which can be found by titration against
standard NaOH solution. But being an acid-catalysed reaction, the acid present originally as catalyst,
also reacts with NaOH solution. Hence a little careful thought reveals that for the same volume of
reaction mixture withdrawn at different time,
Volume of NaOH solution used in Amount of acid present only as catalyst
∝
the beginning i.e. at zero time (V0) (as no CH3COOH is produced at t = 0) (i)
Volume of NaOH solution used at Amount of acid present only as catalyst +
∝
any instant of time (Vt) amount of CH3COOH produced (ii)
Amount of CH3COOH produced
at any instant of time ∝ (Vt – V0) (iii)
(iii) Inversion of Cane-Sugar (Sucrose) : The hydrolysis of sucrose in presence of mineral acid
takes place according to the equation.
(laevo - rotatory)
k= 2.303 a
log
t a–x
we get 2.303 r0 – r∞
k= log
t rt – r∞
Since reactants molecules themselves have energy, so the different between the energy of reactants and
threshold energy should must be provided by effective collisions. This additional energy is called activation
energy (Ea). Thus, higher the activation energy, slower the rate of reaction. The relation between different
forms of energy can be shown by the diagrams.
In Fig (1), energy of reactants (ER) is greater than energy of products (EP) hence ∆H = –ve so this is an
exothermic reaction. Similarly in fig (2), ER < EP ,so ∆H = +ve, This is an endothermic reaction. Thus, we
find that activation energy of endothermic reaction is greater than that of exothermic reaction. So rate of
reaction of exothermic reaction is greater than that of endothermic reaction.
8. ARRHENIUS EQUATION :
k2 Ea (T2 -T1 )
log =
Arhenius proposed an equation to determine activation
k1 energy (Ea)(TatTa) given temperature (T);
2.303R 1 2
K = Ae –E /RT
A = Frequency factor.
On simplifying this equation, we have
! Photosynthesis of HBr has low value of while photosynthesis of HCl has very high value of φ.
Luminiscence : The emission of light during a process other than by the action of heat i.e., emission of
cold light is called luminiscence. This can be of the following different types :
(i) Chemiluminescence : The emission of cold light during a chemical reaction is called chemiluminescence
e.g., glow worm i.e., fire files glow due to oxidation of protein, luciferin present in them. The glow thus
produced in the living organism is called bioluminescence.
(ii) Florescence : Some substances when exposed to light absorb it and immediately start re-emitting it.
The glow continues so long as the light falls on the substance. The glow thus produced is called
fluorescence and the substances producing the glow are called fluorescent substances e.g., fluorite
(CaF2).
(iii) Phosphorescence : Some substances like ZnS continue to glow for some time even after the light is
cut off. Such substances are called phosphorescent substances and the phenomenon is called
Phosphoresence.