CHAPTER 3

COMPLICATED RATE EQUATIONS PROGRAM MAGISTER

SHAFIRA NABILLA
1706082740 DEPARTEMEN TEKNIK KIMIA

3.1. INTEGRATION OF THE RATE EQUATIONS 3.2. OTHER METHODS OF ANALYSIS

The rate depends upon concentration * If 𝑐𝐴 and 𝑐𝐵 both be measured as function of time, a plot of 𝑐𝐴 vs 𝑐𝐵
𝑣(𝑐𝐴 ) allows the rate constant to be estimated. The rate 𝑣(𝑐𝐴 ) is the tangent to the curve
𝑐𝐵0 >𝑐𝐴0 = 𝑘1 + 𝑘2 𝑐𝐵
𝑐𝐴
If pseudo first order 𝑐𝐴 = f(t) at concentration 𝑐𝐴 .
can be established

*Scheme II 𝑒𝑞𝑢𝑖𝑙𝑖𝑏𝑟𝑖𝑢𝑚 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 → 𝑐𝑧𝑒 /𝑐𝐴𝑒 𝑐𝐵𝑒 =𝑘1 / 𝑘−1

k1cA is the chemical flux in the toward direction *Scheme II rate constant → - 𝑑𝑐𝐴 =𝑘 𝑐 𝑐 - 𝑘 𝑐
𝑑𝑡 1 𝐴 𝐵 −1 𝑍 Suppose that reactant B is consumed only in the second order reaction
K-1 is the flux in reverse direction ∆ 𝑑𝑐 𝑑𝑐
Integrated rate equation
ln𝑄+∆ = −𝑘1 𝑄𝑡 + 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 - 𝑑𝑡𝐴 =𝑘1 𝑐𝐴 − 𝑘2 𝑐𝐴 𝑐𝐵 - 𝑑𝑡𝐵 = 𝑘2 𝑐𝐴 𝑐𝐵

* Scheme III 𝑒𝑞𝑢𝑖𝑙𝑖𝑏𝑟𝑖𝑢𝑚 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 → 𝑐𝐴𝑒 /𝑐𝑧𝑒 = 𝑘1 𝑐𝐵0 / 𝑘−1

𝑘1 𝑐𝐴𝑒 = 𝑘1 𝑐𝑧𝑒 At equilibrium
or
𝑐𝐴𝑒 /𝑐𝑧𝑒 = 𝑘1 / 𝑘−1 = K
The differential rate equations are: The differential rate equations are:
𝑑𝑐𝐴 𝑐𝐴
a single reactant undergoes two or more concurrent reactions to give different products = −𝑘1 𝑐𝐴 + 𝑘−1 𝑐𝐵 −𝑙𝑛 = 𝑘1 𝑡 − 𝑘1 𝜃 𝑑𝑐𝐴
𝑑𝑡 0
𝑐𝐴 = −𝑘1 𝑐𝐴 + 𝑘−1 𝑐𝐵
𝑑𝑡
𝑑𝑐𝐵 *Laplace Transform is used
𝑑𝑐𝐵
= 𝑘1 𝑐𝐴 − (𝑘−1 + 𝑘2 )𝑐𝐵 𝑑𝑡
= 𝑘1 𝑐𝐴 − (𝑘−1 𝑘2 )𝑐𝐵 + 𝑘−2 𝑐𝐶
𝑑𝑡
to find 𝑐𝐴 𝑐𝐵 and 𝑐𝐶
𝑑𝑐𝐶 𝑑𝑐𝐶
= 𝑘2 𝑐𝐵 = 𝑘1 𝑐𝐵 − 𝑘−2 𝑐𝐶
𝑑𝑡 𝑑𝑡

𝑑𝑐𝐴
- =𝑘𝑐𝐴 𝐶 𝐶0
𝑙𝑛 1+2𝑟𝐴 𝐶 = - 𝑘1 𝑡 + 𝑙𝑛 1+2𝑟𝐶
𝐴 𝑣 = 𝑘2 𝐾𝑐𝐴 𝑐𝐵
𝑑𝑡 0 0
𝐶𝐴 𝑘1 𝐴 𝐴
𝐹𝑜𝑟 𝑝𝑟𝑜𝑑𝑢𝑐𝑡 𝑌 → 𝐶𝑌 = 𝐶𝑌0 + (1 − 𝑒 −𝑘𝑡
) Showing that the rate of reaction is described by a simple second order rate equation
𝑘
0
*Scheme VIII applies also to a system that includes a reagent
𝐶𝐴 𝑘2 A system of this type is commonly said to possess a fast equilibrium step
𝐹𝑜𝑟 𝑝𝑟𝑜𝑑𝑢𝑐𝑡 𝑍 → 𝐶𝑧 = 𝐶𝑧0 + (1 − 𝑒 −𝑘𝑡 ) if the reagentconcentration is much larger than 𝐶𝐴0
𝑘
*The ratio of product concentrations is equal to the ratio of rate constants,
Independently of time
Steady state approximation (also called the quasi-stedy-state-approximation)
is a powerful method for the simplification of complicated rate equations,
The product of one reaction is the reactant in the next reaction
but because it is an approximation, it is not always valid

Example: The alkaline hydrolysis of a diester Monte Carlo or stochastic method for constructing concentration-time curve:
Frost and Schwemer developed a time-ratio method analogous to Swain’s method is based on the statistics of random event applied to large number
Such method are applicable to kinetic data obtained by titrimetric analysis

in second order condition, in which 𝑐𝐴0 and 𝑐𝐵0 are comparable.

The kinetic problem is greatly simplified if pseudo-first-order-conditions 𝑐𝑅0 > 𝑐𝐴0

are employed, for then Scheme XI bocomes equivlent to Scheme IX
𝑑𝑐𝐴 𝑑𝑐𝐶
= −𝑘1 𝑐𝐴 =𝑘2 𝑐𝐵 𝑐𝐴 = 𝑐𝐴0 𝑒 −𝑘1 𝑡
𝑑𝑡 𝑑𝑡
𝑐0𝑘
𝑑𝑐𝐵 𝑑𝑐𝐷 0
𝑐𝐴 𝑘1 𝑐𝐶 = 𝑘 𝐴−𝑘1 [𝑘2 𝑒 −𝑘1 𝑡 - 𝑘1 𝑒 −𝑘2 𝑡 ]
=𝑘1 𝑐𝐴 − 𝑘2 𝑐𝐵 =𝑘3 𝑐𝐶 𝑐𝐵 = 𝑘 [𝑒 −𝑘1 𝑡 - 𝑒 −𝑘2 𝑡 ] 1 2
𝑑𝑡 𝑑𝑡 1 −𝑘2

𝑐 0 𝑘 𝑘 𝑒 −𝑘1 𝑡 𝑐 0 𝑘 𝑘 𝑒 −𝑘2𝑡 𝑐 0 𝑘 𝑘 𝑒 −𝑘3𝑡

𝑐𝐷 = (𝑘 𝐴−𝑘2 )(𝑘
3
+ (𝑘 𝐴−𝑘1 )(𝑘
3
− (𝑘 𝐴−𝑘1 )(𝑘
2
2 1 3 −𝑘1 ) 2 1 3 −𝑘2 ) 3 1 3 −𝑘2 )