RATE LAW: EFFECT OF CONCENTRATION ON REACTION RATES

Reaction Rates = how we measure rates

RATE LAWS
- how the rate depends on the amounts of reactants
- relationship of reaction rate with concentration of reactants
*LOW concentration = FEWER collisions
*HIGH concentration = MORE collisions

For the generic reaction:

aA + bB + cC o dD + eE
rate D
rate = k

*Rate Law = single reaction & irreversible (only reactants must be considered)
=
=
=
Legends:
k = rate constant (changes with temperature; unique for every reaction)
x = order of reaction with respect to A
y = order of reaction with respect to B
(x + y) = overall order of the reaction

NOTE: x and y are NOT related to a and b. They can only be determined
EXPERIMENTALLY.

Sample Problem 1:
1. For the rate equation: rate = k[ ][ ]
x What is the order of the reaction with respect to A? 1st order wrt A
x What is the order of the reaction with respect to B? 2nd order wrt B
x What is the overall order of the reaction? 1+2 = 3 (3rd order overall)
x What happens to the rate if concentration of B is doubled (keeping constant)?
The rate quadruples
x What happens to the rate if concentration of A is doubled (keeping constant)?
The rate doubles

Set-Up of Reaction Rate Determination

Batch Reactor
x Closed System
x mixture is usually in liquid phase
(density is constant)
x well mixed (A, B, CA, CB and T are
uniform)
x CA, CB and T changes with time

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Reaction Rate Measurement

x Concentration - liquid phase system

x Pressure - gas phase reaction
x Absorbance - colored solution
x Electrical Resistance, pH - ionic reaction

Methods of Initial Rates

Consider the reaction: C4H9Cl(aq) + H2O(l) Æ C4H9OH + HCl(aq)

Time (s) [C4H9Cl] (M) Average Rate (M/s)

0 0.1

50 0.0905 1.9 x 10

100 0.0820 1.7 x 10

150 0.0741 1.6 x 10

200 0.0671 1.4 x 10

300 0.0549 1.22 x 10

400 0.0448 1.01 x 10

500 0.0368 0.8 x 10

800 0.0200 0.56 x 10

10 000 0

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Sample Problem 1:

The overall chemical equation for the reaction of nitrogen oxide, NO with chlorine,
Cl2, is: 2NO + Cl2 Æ 2NOCl. The initial rates of reaction for various concentrations of the
reactants were measured and recorded at constant temperature as follows:

Experiment CNO, M CCl2, M 'CCl2/'

-' 't, M/hr
1 0.25 0.5 0.75
2 0.25 1.0 3.02
3 0.50 2.0 24.10

'CCl2/'t
Convince yourself rave,init = -'

Determine the rate law for this reaction. Calculate the numerical value of the rate
constant. What is the overall order of the reaction? What is the rate of appearance of
NOCl when the initial concentrations of the reactant are CNO = 0.20 M and CCl2 = 0.30 M?

Note: You have to convince yourself that the initial average rate is equal to the rate of
disappearance of Chlorine.

Solution:

To solve for y:
, , (0.25) (0.5)
= =
, , (0.25) (1.0)

, , (0.25) (0.5)
= =
, , (0.25) (1.0)

(0.5)
=
(1.0)

0.75 /ℎ (0.5)
=
3.02 /ℎ (1.0)

= 2.009586049
= 2.0096
= .

To solve for x:
, , (0.25) (1.0)
= =
, , (0.50) (2.0)

, , (0.25) (1.0)
= =
, , (0.50) (2.0)

(0.25) (1.0)
=
(0.50) (2.0)

3.02 /ℎ (0.25)
= (0.25)
24.10 /ℎ (0.50)

= 0.9964126918
= 0.9964 ≈ .

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Determine the Rate Law for this reaction.

Calculate the numerical value of the rate constant.

Select Experiment 1:

= , ,

0.75 = (0.25 ) (0.5 )

ℎ

*The unit of k depends on the order of reaction

What is the overall order of the reaction?

= + =1+2=

What is the rate of appearance of NOCl when the initial concentrations of the reactant are
CNO = 0.20 M and CCl2 = 0.30 M?

Get the initial rate from the given initial concentration.

12
= (0.20 )(0.30 )
ℎ

= 0.216
ℎ
∆
=+
2∆

coefficient of NOCl in the reaction (product side)

∆
= 2( )
∆
∆
= 2 0.216
∆ ℎ

∆
= .
∆

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DIFFERENTIAL METHOD (CONSTANT VOLUME SYSTEMS)

Consider order rate law:

Reaction: →
= − =
Taking the natural log, recall the properties of logarithm:
− = +
Recognize that this is in slope-intercept form = + ; where
− is the y value, is the slope, is the x value and is the y
intercept.

STEPS: How to graph

1. Create the x-y graph where your x is and y axis is .

1
0.9
0.8
0.7
0.6
dCA/dt

0.5
0.4
0.3
0.2
0.1
0
0 0.2 0.4 0.6 0.8 1
lnCA

2. Determine slope = reaction order and the y-intercept which is equal to lnk.

1
0.9
0.8
0.7
0.6
dCA/dt

0.5
slope
0.4
0.3
0.2 ln k
0.1
0
0 0.2 0.4 0.6 0.8 1
lnCA

However, we are usually given concentration as function of time from batch

reactor experiments.
time (s) 0
concentration

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 Sample Problem 1:
The reaction of triphenyl methyl (trityl) chloride (A) and methanol (B)
( ) + → ( ) +
+ → +

It was carried out in a solution of benzene and pyridine at 25℃. Pyridine reacts
with HCl that precipitates as pyridine hydrochloride thereby making the reactions
irreversible. The concentration to time data below was obtained in a batch
reactor.

time (min) 0 50 100 150 200 250

Concentration of A ( / × 10 ) 50 38 30.6 25.6 22.2 19.5

3
The initial concentration of methanol was 0.5 / .

a. Determine the reaction order with respect to A.

b. In a separate set of experiments, the reaction order with respect to B was
1 order. Determine the value of k.

Solution:
For part a. Determine the reaction order with respect to A.

1. Postulate a rate law.

=

2. Process the data in terms of the measured variable.

In this case:

3. Look for simplifications.

For example, the date given is at / × 10
time (min) 0
Concentration of A ( / × 10 ) 50
Now,
time (min) 0
Concentration of A ( / ) 50 × 10
Therefore, = 0.05 / 3.
3
Given that = 0.5 / which is the concentration of methanol given.
Comparing , we can assume that is so small to affect the
concentration of B, as it is 10 times smaller. In that notion, we can also
assume that is constant at any point of time = .

4. Relate step 1 and 3

= =
We can let another constant to represent since we understand
that it is a constant value. The reaction will therefore have ‘pseudo order’
that is with respect to A.
=
Therefore,
= ′

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 5. The rate equation will become:
=− = ′

6. Take the natural log of both sides

− = +
Recall: Recognize that this is in slope-intercept form = + ; where
− is the y value, is the slope, is the x value and ′ is the y
intercept.

7. Find − as a function of from the concentration-time data.

Graphical Method
∆ −
− =
∆ −
time (min) ( / × 10 )
0 50
50 38
100 30.6
150 25.6
200 22.2
250 19.5

∆
Solve for − ∆
at EACH STEP of time.
Example for:
time (min) ( / × 10 ) ∆ − 38 − 50
− = = = 0.24
0 50 ∆ − 50 − 0
50 38
I
∆
It’s been a practice to multiply − ∆
values to 10 to scale those values easier as
we graph them later, also called normalizing values. Therefore,

∆ 0.24 × 10
− × 10 = = 2.4
∆ 10

Notice that we also divided the value by 103, because according to the data given
those concentrations in the table are at mol/dm3×103

∆
time (min) ( / × 10 ) − × 10
∆
0 50 -
50 38 2.4
100 30.6 1.48
150 25.6 1.0
200 22.2 0.68
250 19.5 0.54

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 ∆
Plot − × 10 .
∆

Recall Equal Area differentiation approach in Advance mathematics to

solve for the area under the curve.

2.5

2
∆
− × 10 1.5
∆
1

0.5

0
0 50 100 150 200 250 300

(min)

Draw a curve in the graph in such a way that it will cut through the points equally.

3
These areas are equal
2.5

2
∆
− × 10 These pair of areas are equal
∆ 1.5

0.5

0
0 50 100 150 200 250 300

(min)

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Get the instantaneous rate at each point of time which is the y-values of intersection of
the curve to time for each step, which are shown as red dots in the illustration below.
3

2.5

∆ 2
− × 10
∆
1.5

0.5

0
0 50 100 150 200 250 300

(min)

time −
∆
× 10 ( / − ) − × 10 ( / − )
( / × 10 )
(min) ∆

0 50 - 3.0
2.4
50 38 1.75
1.48
100 30.6 1.25
1.0
150 25.6 0.8
0.68
200 22.2 0.55
0.54
250 19.5 0.47

Plot the − × 104 vs ln ( × 10 )

− × 10 − × 10 × 10 ( × 10 )
3.0 1.0986 50 3.912
1.75 0.5596 38 3.6375
1.25 0.2231 30.6 3.4210
0.8 -0.2231 25.6 3.2425
0.55 -0.5978 22.2 3.1001
0.47 -0.7550 19.5 2.9704

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Use Microsoft excel to generate the equation of the linear regression to determine the
slope.

Now, determine the order and k of the reaction:

− = +
The order of reaction, which is x according to the equation of the line is approximately
equal to 2 with respect to A.

Solution:
For part b. In a separate set of experiments, the reaction order with respect to B was
1 order. Determine the value of k.
− × 10 − × 10 × 10 ( × 10 )
3.0 1.0986 50 3.912
1.75 0.5596 38 3.6375
1.25 0.2231 30.6 3.4210
0.8 -0.2231 25.6 3.2425
0.55 -0.5978 22.2 3.1001
Recall:
0.47 -0.7550 19.5 2.9704

=− = ′
Choose any point from the table of the measured data. For example:
− × 10 − × 10 × 10 ( × 10 )
0.55 -0.5978 22.2 3.1001

Use the true values at this point and substitute to the rate law equation to solve for k’.

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 − = ′

5.5 × 10 = 0.222
−
= 0.1116
−

Note: unit of k varies depending on the order or reaction.

NOW, recall that =

= Note: The right term is raised
to 1 as it is the order of
. = . reaction in terms of B as
− instructed by the problem.

= 0.2232

ADDITIONAL NOTE:
We can solve for the rate of the whole reaction from all the data that we’ve gathered.

= 0.2232

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POLYNOMIAL FIT FOR DIFFERENTIAL METHOD OF KINETIC ANALYSIS

Sample Problem 1:
The reaction → 2 is carried out in a constant volume batch reactor at 25⁰C.

CA ( ) t (s) From the given concentration-time data,

0.1 0 determine the order of the reaction. Use the
0.0905 50 polynomial fit method.
0.082 100
0.0741 150 Rate Law: = − =
0.0671 200
0.0549 300 Linearization: − = +
0.0448 400
0.0368 500
0.02 800
0 10000

Step 0. Prepare a graphing software to use (i.e. MS Excel, PolyMath, OriginLab)

Step 1. Postulate the rate law.
= − = (1)
Step 2. Linearize.
− = + (2)

Step 3. Assume a polynomial function/model.

= + + + + + ⋯ (3)

Step 4. Solve for the derivative of the model.

= +2 +3 +4 + ⋯ (4)
Step 5. Plot (assign as y and as x)

To navigate in MS Excel:
Insert > Charts > Scatter > Select Data > Add x & y values (Optional)
Chart Design > Axis Title

To Expose R2:
Click Data > Right Click > Add Trend Line > Polynomial > Display
Equation on Chart > Display R2 on Chart

To determine the best polynomial fit:

Click Data > Right Click > Add Trend Line > Polynomial > Add counting
numbers
Condition: R2 must be close to unity (1).

The lowest counting number to reach unity is the best polynomial fit.

Substitute the polynomial equation on MS Excel to Equation 3.

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 Proceed to Step 4 (solve for the derivative of the model)

Solve for every instantaneous rate (using the time given)

Linearize the concentration rates and instantaneous rates − .

Plot − vs .

To check linear fit:

Click Data > Right Click > Add Trend Line > Linear > Display Equation on
Chart > Display R2 on Chart

Establish linear fit model from linear fit results.

CA (mol/L) t (s) -dCA/dt ln(-dCA/dt) ln(CA)

0.1 0 0.0002 -8.517193 -2.30259
0.0905 50 0.000181 -8.619641 -2.40241
0.082 100 0.000162 -8.727297 -2.50104
0.0741 150 0.000145 -8.840675 -2.60234
0.0671 200 0.000128 -8.96036 -2.70157
0.0549 300 9.89E-05 -9.221401 -2.90224
0.0448 400 7.36E-05 -9.516866 -3.10555
0.0368 500 5.25E-05 -9.854697 -3.30226
0.02 800 1.44E-05 -11.14828 -3.91202
0 10000

Rate Law: = − =

ln − = ln + ln

= + + + +

= + 2 + 3 + 4

0.12
y = -7E-11x3 + 2E-07x2 - 0.0002x + 0.1
0.1
R² = 1
0.08
CA (mol/L)

0.06

0.04

0.02

0
0 200 400 600 800 1000
t (s)

= 0.1 − 0.0002 + 2 × 10 − 7 × 10
= −0.0002 + 4 × 10 − 2.1 × 10

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 − = 0.0002 − 4 × 10 + 2.1 × 10

ln − = ln + 1.5986 ln

0
-5 -4 -3 -2 -1 0

-2

y = 1.5986x - 4.6968 -4
R² = 0.9785
ln(-dCA/dt)

-6

-8

-10

-12
ln(CA)

Numerical (Finite-Difference Method)

This method can only be used when the data points in the independent variable
(t) are equally spaced.

The three-point differentiation formulas:

Initial point: = ∆

Interior point: = ( ) − ( )
∆

Example: = [ − ]
∆

Last point: = ( ) − 4 ( ) + 3
∆

Example: = ∆
[ − 4 +3 ]

PROBLEM SET NO.1

Hand write and answer each problem. Provide Excel file/s for finite difference and
polynomial fit methods.

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 1. A gaseous reaction: 2A (g) + B (g) ⟶ 2C (g) showed a decrease in pressure from
120 mm Hg to 100 mm Hg in 10 minutes. What is the rate of appearance of C?
Answer: 4 mm Hg/min

2. The liquid-phase bromination of acetone is acid-catalyzed:

CH3COCH3 + Br2 ⟶ CH3COCH2Br + H+ + Br-
The rate of bromine was measured for several different concentrations of acetone,
bromine, and H+ ions at a certain temperature:

[CH3COCH3] Br2 (M) [H+] (M) Rate of

(M) Disappearance
of Br2 (M/s)
(1) 0.450 0.0450 0.0450 5.97 x 10-5
(2) 0.450 0.090 0.0450 5.97 x 10-5
(3) 0.450 0.0450 0.090 1.19 x 10-4
(4) 0.599 0.0450 0.180 3.17 x 10-4
(5) 0.599 0.0450 0.0450 7.94 x 10-5

(a) What is the rate law for the reaction? (b) Determine the rate constant.

3. T-butyl bromide is converted into t-butyl alcohol in a solvent containing 90 percent

acetone and 10 percent water. The reaction is given by

(CH3)3CBr + H2O → (CH3)3COH + HBr

The following table gives the data for the concentration of t-butyl bromide versus
time:

t,min 0 9 18 24 40 54 72 105
(CH3)3CBr 0.1056 0.0961 0.0856 0.0767 0.0645 0.0536 0.0432 0.0270
(mol/L)

What is the order of the reaction? What is the rate constant of the reaction? Use
graphical and polynomial fit (3rd order) differential method. You should provide the
following sample table for comparison of the methods:

Answer: Data fits to First Order

4. To study the photochemical decay of aqueous bromine in bright sunlight, a small

quantity of liquid bromine was dissolved in water contained in a glass battery jar and
placed in direct sunlight. The following data were obtained at 25 oC:

Time (min) 10 20 30 40 50 60

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 Ppm Br2 2.45 1.7 1.2 0.88 0.62 0.44

Determine whether the reaction rate is zero, first, or second order in bromine, and
calculate the reaction rate constant in units of your choice. Assuming identical
exposure conditions, calculate the required hourly rate of injection of bromine (in
pounds) into a sunlit body of water, 25,000 gal in volume, to maintain a sterilizing
level of bromine of 1.0 ppm. Use finite difference differential method.

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THE INTEGRATED RATE LAW: CONCENTRATION DEPENDENCE ON TIME

Integrated Rate Law – shows how the concentrations of species in the reaction
depend on time

Reaction Order Rate Law

First Order kCA
Second Order kCA2
Zeroth Order kCA0

First Order Reaction

Reaction that depends on only one reactant (unimolecular)
Dimerization of butadiene:

2 ( )
→ ( )
(other reactants can be present but is in zeroth order)

Rate Law: = (can only be determined only by experiments)

Integrated form in terms of Concentration:

Derivation:
Rate Law:
−
=

=−

=−

=−

ln | =− |
0
ln − ln =−

Integrated form in terms of Conversion:

From stoichiometry
= =

=
= (1 − )
since it is in constant volume, then = :

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 ( )
=
= (1 − ) (only possible if the volume is constant)
= (1 − ) = −
get the derivative
=− (plug in to the rate law equation)
=
( )
= (1 − )
= (1 − )

( )
=

∫ ( )
= ∫
= 1−
= −
∫ = − ln +

− ln|1 − = | | |
0 0
− ln|1 − | − (− ln|1 − 0|) − ln|1 − 0| =
− ln|1 − | =

Half-life form: ⁄ =

Example: First Order

The first order dimerization of butadiene was studied at 500 K: 2 ( )
→ ( )
. The
following data were obtained
Time (s) [ ] (mol/L)
195 1.6 × 10
604 1.5 × 10
1246 1.3 × 10
2180 1.1 × 10
6210 0.68 × 10

a. Determine the k of the reaction

b. How many hours would one have to wait in order to obtain 60%
dimerization?
c. What is the half-life of the reaction?
d. What is the concentration of butadiene after five half-lives?

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 Solution:
a.)

Determine the k of the

reaction
0
-1 0 2000 4000 6000 8000
-2 y = -0.0001x - 4.1432
R² = 0.9852
-3
-4
-5
-6

(not accurate if the value is so small use regression analysis)

ln = − + ln
=− +
= 0.000135741294390876
= . × = . ×

b.) Using Concentration Form:

= (1 − 0.6)
= 0.4

ln = ln −
ln(0.4 ) = ln − (1.3754 × 10 )
0.4
ln = − (1.3754 × 10 )

ln(0.4) = −(1.3754 × 10 )
= . = .

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 Using conversion form:
− ln( 1 − ) =
− ln( 1 − 0.6) = (1.3754 × 10 )
= . = .

c.)
, ⁄ = 0.5
ln = ln − ⁄
ln(0.5 ) = ln − ⁄
0.5
ln =− ⁄

ln(0.5) = ⁄
ln 2
⁄ =
ln 2
⁄ =
1.3754 × 10
⁄ = . = .

d.)
After 1 half-life: = =
After 2 half-lives: = = =
After 3 half-lives: = = =
After 4 half-lives: = = =
After 5 half-lives: = = =

Determine using from the given data

ln = ln −
use: = 195 and = 1.6 × 10

ln 1.6 × 10 = ln − (1.3754 × 10 )(195 )

= 0.01664291635

=
2
0.01664291635
=
32
= . ×

Second Order Reaction

Comprised of 2 cases:

Case 1: With identical reaction

+ →
- Bimolecular reaction (2 reactant molecules: identical)

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 2 ( ) → 2 ( ) +2 ( )

- Rate is directly proportional to the square of the concentration of one

of the reactants.

Case 2: With different reactants

+ →
- Rate is proportional to the product concentrations of the two reactants.

For Case 1: With identical reactant

Rate Law:
− =

Integrated Rate Law:

1 1
= + ∶

= ∶
1−

Half-life Form:
1
=

Where in:
= Concentration of A at time t
= rate constant
= time
= Initial concentration of A
= Half-life
= Conversion of A

Derivation

− =

= −

1
− | = |

1 1
− − =−

1 1
= +

y b mx

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Second Order Reaction Derivation of Integral Rate Law in terms of Conversion

= (1 − )= − Plug in to rate
=−
(differential) law
Rate Law:

− = = (1 − ) ∫ ( )
= ∫
=1−
=−

1
− = +

1
| = |
1−
=1

− =
=0
1−1+
=
1−

=
1−

y m x

Sample Problem 1:

At 25oC, the second order reaction 2 ( ) 2 ( ) +2 ( ) is 30%

complete after 5.82 hours when the initial concentration of is 4.46 .
a. How long will it take for the reaction to be 75% complete?
b. What is the half-life of the reaction?

Solution:

a.
= 0.30, = 5.82 ℎ
= 4.46

=
1−

0.30
= 4.46 (5.82 ℎ)
1 − 0.30

0.0165
= .ℎ

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 =
1−

0.75 0.0165
= .ℎ
4.46
1 − 0.75

= .

b.

, = 0.50

For 2nd order: ,

= +

1 1
= +
0.50

1 1
− =
0.50

− 0.50
=
0.50

0.50
=
0.50
1
=

1
=

Note: Half-life for 2nd order reaction depends on the reaction rate constant and the
initial concentration of the reactant.

1
=
0.0165
4.46 .ℎ

= .

Sample Problem 2:

At 25°C, the second-order reaction 2 ( ) →2 ( ) +2 ( ) is 50%

complete after 5.82 hours when the initial concentration of is 4.46 . What
is the half-life of the reaction?

Solution:

Note: Since it is stated in the problem that the reaction is 50% complete after 5.82
hours,

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 / = 5.82 ℎ

Note: For a single and identical reactant type of reaction, the time to achieve a
50% conversion is the half-life of the reaction. For a different reactant type of
reaction, the time to achieve a 50% conversion of the limiting reactant is the half-
life of the reaction.

Zero Order reaction

This type of reaction takes place when a catalyst is required for a certain
reaction to occur.

Note: The overall reaction rate will be limited by the value of the rate constant.

Rate Law:
− = =
Integrated Form:
= −
Half-life Form:

/ =
2

Where in:
= concentration of A at time t
= rate constant
= time
= initial concentration of A
/ = half-life
= conversion of A

Summary of Kinetics of Zero-Order, First-Order, and Second-Order Reaction

Concentration-Time Equation
Order Rate Law Half-Life

0 = = − =
2
2
1 = = − =

1 1 1
2 = = + =

In case the order of reaction is not given, you can use the integrated rate
law to evaluate the order of reaction in the problem.

37 | The Integrated Rate Law: Concentration … | ChE 417 | RDMaalihan | BSChE Batch 2018
 Sample Problem: Decomposition of H2O2
[ ] (min)

0.300 M 0

0.221 M 1

0.107 M 5

0.065 M 10

0.047 M 15

0.037 M 20

Zeroth Order
0.3

0.25
R² = 0.7721
Hydrogen Peroxide
Concentration (M)

0.2

0.15

0.1

0.05

0
0 5 10 15 20
-0.05
Time (minutes)

First Order
0
0 5 10 15 20
-0.5

-1
R² = 0.9308
-1.5
ln [H2O2]

-2

-2.5

-3

-3.5

-4
Time (minute)

38 | The Integrated Rate Law: Concentration … | ChE 417 | RDMaalihan | BSChE Batch 2018
 Second Order
30

25
R² = 0.9999
20

1/H202
15

10

0
0 5 10 15 20
Time (minute)

Note: To determine the order of reaction of decomposition of H2O2, graph the given
Concentration-Time data and get the R-squared of each order reaction using
regression analysis. The order of reaction of the decomposition of H2O2 will be the
order of reaction having R-squared value near unity.
Since second order has the value nearest to unity, it is rightfully to say that
the decomposition of hydrogen peroxide (H2O2) obeys second order kinetics.
Rate = kCH2o22

Sample Problem 1:
The half-life period of a first order chemical reaction is 6.93
minutes. The time (minutes) required for the completion of 99% of the
chemical reaction will be:
= 6.93
= 0.99
ℎ =?

Solution:
ln(2)
=
ln(2)
6.93 =
= 0.1000212382

− = (1 − ) = −
− = (1 − 0.99) = (0.1 )( )
= 46.04192338
= .

39 | The Integrated Rate Law: Concentration … | ChE 417 | RDMaalihan | BSChE Batch 2018
 Sample Problem 2:
The data at the left were collected in a study of the photochemical
degradation of ozone, O3, by light. Analysis of the data gave a straight- line
relationship when the C03-1 was plotted versus time.
2 ( ) 3 ( )
Time (s) (O3) (M)
0 2.98 x 10-3
50 2.40 x 10-3
100 1.90 x 10-3
150 1.60 x 10-3
200 1.35 x 10-3
250 1.18 x 10-3
300 1.07 x 10-3
400 8.65 x 10-3

Calculate the concentration at 523 s. Answer: C03 = 7.05 x 10-4 M

Solution:

Reaction is 2nd Order: = +

Where: = ; = ; = ; =

Using Excel plot the given data and perform linear regression.

By Linear Regression:

.
Based on the linear equation: = =
∙

Generally: unit of k is for an nth order of reaction.

( )

Thus, for 2nd Order: ( )

= ( )

Substitute the values:

1 1
= +

40 | The Integrated Rate Law: Concentration … | ChE 417 | RDMaalihan | BSChE Batch 2018
 1 1 2.0709
= + (523 )
2.98 × 10 ∙

= 7.0489492 × 10

= . ×

Sample Problem 3:
The time for half-life period of a certain reaction A Æ Product is 1
hour when the initial concentration of the reactant ‘A’ is 2.0 mol L -1, How
many hours does it take for its concentration to come from 0.50 to 0.25 mol
L-1 if it’s a zero-order reaction?
= 1ℎ

=2

0.5 → = 0.25 =?

Since it is in zero-order reaction

The half-life equation is:
=
2
=
2

2
=
2(1 ℎ )
=1
−ℎ

And for the integrated rate law equation

= −
0.25 = 0.5 − 1
−ℎ
0.25 − 0.5
=
−1
−ℎ
= .

41 | The Integrated Rate Law: Concentration … | ChE 417 | RDMaalihan | BSChE Batch 2018