INTRODUCTION

Pseudo first order reaction rate constant (K0) for the reaction of CO2 with sterically hindered secondary
amine at given temperature of 293-313 kelvin and various amine concentrations were examined

Reaction mechanism were also proposed on basis of second order kinetics

The termolecular mechanism was appropriate fit to the experimental data for predicted CO2 absorption rates
of MAE and EAE with absolute average deviation of 2.81% and 14.91% respectively.

On basis of BASE CATALYZED reaction mechanism is more precise in term of hindered amines IPAE and TBAE

Considering the reactions following are the mechanism that were presented

1. BASE CATALYZED REACTION

2. TERMOLECULAR MECHANISM

These mechanism were used to predict and interpret the experimental value of CO2 kinetics of absorption
to validate the possible reaction pathway involved in the reaction between CO2 and aqueous solution of
hindered amine

BASE CATALYZED MECHANISM

Base catalyzed reaction means that aqueous solution act as base in reaction. In present case of study of
reaction of C02 with the amines this role of base is played by the amine which are tertiary amines in present
case. Here tertiary amine do not react with the C02 instead act as base in aqueous solution for transformation
of CO2 to the bicarbonates as given by following reaction

CO2+R3N+H2O== R3NH+ +HCO3_

KINETICS
All possible reaction that exist in the reaction of CO2 with aqueous solution of hindered amine are proposed
as follow

In evaluating the pathway used to derive the kinetics, all possible Chemical reactions that exist in the
reaction of CO2 with aqueous Solution of hindered amines were used. These are listed in equations.in these
reactions R2NH, CO2, R2NCOO-, HCO3-, H20 undergoes the reaction with rate constants.
Ka,K2,K3K4,KH2O,K5,K6,K7. R is alkyl group bonded to NH- group. R2NH represents the amines which are
sterically hindered amines. In the equations given below K2 is the second order reaction rate constant of
CO2 reacting with an amine where as KH2O is the reaction rate constant between CO2 and H2O and KOH-
represents the reaction rate constant of CO2 with OH-.

Following the given reactions of sterically hindered amines with CO2 rate equation will be developed on the
basis of assumption made in neglecting the rate constant which have comparatively low value as compared
to rate constants of reactions which dominate the absorption reactions of CO2 with sterically hindered
amines.

RCO2=K0[CO2]={ Kamine [R3N] + Koh- [OH-] +kh20 [H20]}

[CO2]
By observing the rate equation we recognize that the rate equation does not include the effect of K4. That’s
why its rate is omitted in the final rate expression. As hydroxyl ions are also present in small amount so there
rate constant can also be neglected.

So the final rate expression is as follow

RCO2=K0 [CO2] =K2 [R3N][CO2]

Where

N= AMINES

K0=K2 [R3N]

TERMOLECULAR MECHANISM
Amine reacts with one molecule of CO2 and one molecule of base in a single reaction

CO2 + AmH……….B==AmCOO- …………BH+

According to this mechanism the CO2 absorption rate can be expressed as

RCO2 = K0[CO2] = {Km[Am+Koh[OH]+K[H20]}[CO2][AmH]

Data was collected using stopped flow technique

CO2 was bubble through the absorption cell which already contained the sterically hindered amines.
Temperature of absorption cell was controlled by thermostat. Value of partial pressure was recorded at
different intervals for CO2 which was measure of progress of rate of reaction. Through control loop this
partial pressure was converted into voltage.

Following are the conclusions/observations we can infer from the graph given above

1. Conductivity gives us the measure of change in concentration

2. Conductivity approximately varies linearly with the time
3. Data points passed through the straight line
4. So it means that rate of reaction is proportional to first power of concentration that’s why we obtain
straight line graph from experimental data
5. Standard deviation is 0.9937
6. First order is fitted

Hence we come to know that absorption of CO2 with sterically hindered amines fit the rate equation and has
been validated with given standard deviation. Rate of absorption of C02 was linear depend on first power of
CO2 concentration.
Following data shows the plot of observed pseudo first order rate constant against amine concentration at
T=313 k. MEA, MDEA, MEA, EAE, IPAE and TBAE are sterically hindered amines. This graph also validates
pseudo first order kinetics. On x axis is concentration of amine in mole/m3 on y axis is given the value of rate
constant in second inverse.

All of the plots are linear which shows that rate constant variation as function of concertation at constant
temperature.