Reactions and Reaction Rates- Definitions

Role of chemical reactions- Definitions

Chemical kinetics- rate

Chemical reactors
Stoichiometric notation
Extent of reaction and law of definite
proportions
Single rxns, multiple rxns

Role of chemical reactions- Definitions

Defn. of rxn rate

Species dependent definition
Single fluid phase
Multiple phases
Heterogenous catalysis
Species independent definition

Reaction rate -definition

-ri = rate of disappearance of i (moles i
consumed/time) /unit (something)
(Something) = volume of reactor, weight of
catalyst,surface area of the packed bed, volume of
packed bed

tableun_01_01

tableun_01_02

Reaction RatesSome Generalizations

Rates of reaction
-ri = rate of disappearance of i (moles i consumed/time) /
/unit (something)
(Something) = volume of reactor, weight of catalyst,surface
area of the packed bed, volume of packed bed
Usually ri = f (concentration: Ci ,T, P, [homogenous rxns] , Ci,T, P + mass
trnsfr+ heat trnsfr)

-ri =(dNi/dt)*1/Vr ri =(dNi/dt)*1/W; -ri =(dNi/dt)*1/S;

-ri=(dNi/dt)*1/VP

Generalisations
First generalisation -ri = f(T)f(Ci): separation of

variables basis of collision theory CT and

transition state theory TST
Second generalisation: k(T) = A exp(- E/RT)

Arrhenius relationship from thermodynamicseasier to visualise from TST

Boltzmann distribution

Transition state theory

Transition state theory

Boltzmann distribution- K.Jackson

Temperature: kT= mv2 most probable velocity of atoms
Consider atoms in a gravitation potential field, then F=mg;
PV=NRT, P= nkT: n=N/V where n is atoms per unit volume
dP= kTdn ; dP = Ph+dh Ph = -mgndh and hence upon
combining dn/n =(mg/kT)dh leading to n = n exp(-P.E./kT).
The K.E. distbn may now be derived by examining K.E. of an
atom at height zero to reach ht h- requires a K.E. > P.E. at ht h
with an upward velocity > u ie nv>0 =nv>u(0) thus
{nv>u(0)/ nv>0(0)} = exp[-mgh/kT] = exp[-K.E./kT]

fig_02_02

Effect of Tempreature on reaction rate constant

Third generalisation: Reaction rate is proportional to

concentration

fig_02_03

Fourth generalisation: F (of all Ci) =iCi i

Fifth generalisation:
If a reaction is reversible the net rate is the
difference between the forward and the reverse
reaction.
The form of the reverse reaction must be
thermodynamically consistent i.e the expression
for the net rate of a reversible reaction must
reduce to the equilibrium expression when the
net rate is zero

Thermodynamics and kinetics

Thermodynamics usually
deals with reversible
processes , processes
under equilibrium
conditions
Kinetics deals with rates
of conversions,
irreversible processes,
processes designed on
economic considerations
Rate at equilibrium will
tend to zero.