PHYSICAL CHEMISTRY

CHM 101/CHEMISTRY DEPARTMENT

DR. MRS BAMGBOSE

1
 CHEMICAL KINETICS
In kinetics, the following questions are important.
How far does the reaction go and what is the position of equilibrium?
Thermodynamics deals with energy associated with equilibrium called
Gibbs free energy (G).
The free energy change, G  RT ln K eq .
Where Keq is the equilibrium constant.
G that
 ve eq  1 (large),
it implies
When the
, Ksystem is at equilibrium.
G  ve, K eq  1 (small) and G  0 ,
How fast does the reaction go? This is the concern of kinetics.
Kinetics also examines the detailed pathway that a reaction goes through
in going from reactants to products.
Thus giving us an insight into the reaction mechanism.
The rate of chemical reactions is usually followed at constant temperature
by measuring:
either the decrease in concentration of the reactants

or an increase in the concentration of the products with time.

A unit of rate is s-1 for a first order, or Ms 1 ( moldm 1s 1 )

for a second order reaction.
Measurements of reaction rates
It is usual to conduct a preliminary investigation to establish:-
(1) The nature and extent of possible side reaction
(2) The position of equilibrium
(3) That the reaction proceeds at a conveniently measurable rate
The rate is then measured at constant temperature by one of the
following methods which allow the concentration of either reactants
or products to be followed with time.

METHODS USED IN MEASURING RATES OF CHEMICAL

REACTION

Volumetric or Gravimetric Analysis:

As in ester hydrolysis where samples may be titrated against standard
alkali to determine the concentration of acid produced.
Measurement of Pressure Change:
In a gaseous system reacting at constant volume requires that the
reaction leads to a change in the total number of molecules present

Measurement of Change in some Physical Property:

Related to reactant or product, concentration or both e.g. refractive
index, specific volume, colour intensity, specific conductance,
viscosity, specific rotation (plane of polarised light if the
compound are optically active) and thermal conductivity.
Analysis of Experimental results

Considering The Rate Expression

A  B  Product
 d A   d B d P
Rate     k A B, k = rate constant ( M 1s 1 )
dt dt dt
Since A  and B decreases with time, rate must also decrease.

The rate constant, k , remains unchanged throughout the reaction.

It also provides a more convenient measure of reaction velocity than does the experimentally
measured.
Rate Law: - Expression which gives the rate of reaction as a function of the concentrations of
some of the reactants.

dx
e.g.  k A B etc. which is rate law, k = rate constant.
dt
A or B = concentrations of A or B .
Order of a Reaction: This is the sum of the power of the concentration terms in the differential
rate law or in the rate determining step.

This is experimental quantity which cannot be predicted from the equation of the reaction.
 Differential Rate Equations

d P 
If experimentally we found that  k A  , the reaction is 1st order,
dt
k is first order rate constant.
d P
 k A B , overall reaction is 2nd order; k is second order rate constant.
dt
d P 
 k A  B , k is 2nd order with respect to A or B but overall order is 4th order.
2 2
If
dt

reaction is 3rd order, k is 3rd order rate constant.

The order of the reaction does not follow from stoichiometry.

This shows that the reaction is not elementary- It occurs in a series of consecutive steps
(mechanism) the sum of which represents the overall stoichiometry.

In such a case, some steps are slow while others are fast. The slowest step is called the rate-
determining step. E.g.
Molecularity: - This is the number of chemical species which are involved in the rate
determining step. It is a theoretical quantity 1, 2, 3, unimolecular, bimolecular and
termolecular.

E.g. thermal decomposition of acetaldehyde

CH 3 CHO  CH 4  CO

3KClO  KClO 3  2KCl, (Termolecu lar)

KClO  O 2  KClO3 , (Bimolecul ar)

2 N 2 O 5  4 NO 2  O 2 , (Unimolecu lar)

2 NO  O 2  2 NO 2 , (Termolecu lar)
To show the mechanism, let consider the unimolecular decomposition of N 2 O 5 .
N 2 O 5  N 2 O *5 (Unstable i.e. energised molecule and rate determining step)

N 2 O *5  NO 2  NO 3 , (Fast)

Each of these steps is an elementary step.

Derivation of Rate Equation by Integration Method

Lets consider:

First order rate equations, A  Products

At time, t  0 a 0

tt ax x
  d A   d a  x 
Rate    k1 a  x 
dt dt

dx
Rate   k a  x 
dt

dx
 kdt
ax

x dx t

o ax
=  kdt
0

 ln a  x   kt  c , when , x  0, t  0, c  lna and by substitution,

 ln a  x   kt  ln a
ln a  l a  x   kt

a
ln  k1 t , where k  rate constant or
ax
 k1
A plot of log a  x  versur t gives a straight line with slope   and intercept  log a .
2.303
A  B  C  Product

If experimentally we found that:

d P 
(i) Rate 
dt
 
 k moldm 3 s 1 . This indicates that the reaction is zero order i.e. it does not

depend on the concentration of any of the reactants, k  zero order rate constant.

d P
(ii) Rate 
dt
 
 k A  moldm 3 s 1 . The reaction is first order, k  first order rate constant (

s 1 )

d P
(iii) Rate 
dt
2 2
 
 k A B or k A  or k B moldm 3 s 1 . The reaction is second order,

  
k  mol 1dm 3 s 1 or M 1s 1 
d P
(iv) Rate 
dt
2 3
 
 k A BC or k A  B or k A  moldm 3s 1 . The reaction is third order,

   
k  mol 2 dm 6 s 1 or M 2 s 1 .
Half-life: The time taken for half of the reactants to go to products designated by t 1 .
2

a a
t 1  a  x    , x   
2 2 2

 
a
kt 1  2.303 log   2.303 log 2  0.69
a
2
 
2

0.69
t1  .
2
k1

Half-life period of any first order reaction is independent of the initial concentration i.e. it takes
a

First order reaction just as much time to go halfway to completion when the initial
concentration is high as when is low.

Second order rate equations

When A and B are the same i.e. of the same concentration

2A  Product , e.g. Dimerization of butadiene 2C 4 H 6  C 8 H 12

A  B  Product

2A  P

a 0 when t  0

ax x When t  t

d A 
 k A 
2

dt

d a  x  dx
 k a  x  
2
  kdt
dt a  x 2

x dx t
Integrate  a  x 
0 2
  kdt
0

Let (a  x)  u ,  dx  du or dx   du

x  du t
0 u2
 0 kdt

  u  2 du  k  dt
x t

0 0

u 21  t 01 
  k  
 2 1  0 1
 1
Plot of against t gives a straight line with a slope  k 2 .
a  x 
When A and B are different i.e. not the same concentration

A  B  Product

a b 0 when t  0

a  x  b  x  x When t  t
 2.303  ba  x  
k2  log 
t a  b   a b  x  

 ba  x  a  b k 2 t b
log     log
 a b  x  2.303 a

 ba  x  a
Plot of log   against t gives slope  k 2 and intercept  log  .
 a b  x  b
Experimental determination of order of reaction

Experimentally when a reaction involves two reactants, the reaction is carried out by keeping
one of them constant and then varying the other and the rate increases in proportion to the
increase in the concentration of the varied reactant.

Examples

Rate A
1  10 2 0.1

2  10 2 0.1

3  10 2 0.3

It means is directly proportional to concentration of A , meaning that the rate is first order with
respect to reactant A i.e. R A 
 Rate A
1  10 2 0.1

4  10 2 0.2

9  10 2 0.3

It means that R A 2 which shows that rate is second order respect to reactant A .

Rate ( M 1s 1 ) A (M) B (M)

1.2  10 2 1.0 1.0

4.8  10 2 1.0 2.0

2.4  10 2 2.0 1.0

For the experiment we do not know the order. But the way to write the rate eqn is
R  k A  B . Considering experiment (i) & (ii) where [ A ] is constant and [ B ] is varied,
x y

R ii 1.0x 2.0y 4.8  10 2

 
Ri 1.0 1.0 1.4  10 2
x y

2.0y 4
y2

It is shows that the order with respect to B is second order and R  k B2 . Consider experiment
(i) & (iii),

R iii 2.0x 1.0y 2.4  10 2

 
Ri 1.0 1.0 1.2  10 2
x y

2.0x 2
x 1

It means the rate is first order with respect to A and R  k A  . The overall rate equation for
the reaction is R  k A B2 , hence the overall order of the reaction is third order.
If we are to calculate the rate constant, we can take any experiment as follows,
R  k A  B  k A B
x y 2

R  k 1.01.0
2

k  1.2  10  2 mol  2 dm 6 s 1

For experiment 2

R  1.02.0
2

4.8  10  2  k  4
4.8  10  2
k  1.2  10  2 mol -2 dm 6 s -1
4

The third experiment also gives similar result showing that the rate is constant all through.

Determination of Order of Reaction

Integration Method: - This involves calculation or graphically determination of the order by

finding the reaction rate constant k . The experimental concentration-time data are substituted
into the integrated rate equation e.g. first, second and third orders of the reaction etc. The
independent rate constant corresponding to each concentration-time datum will be
approximately the same if the correct integrated rate equation is used but if the wrong equation
is used, constant value for k will not be obtained. If graphical method is employed a straight
line will not be obtained, if wrong equation is used.
Question 1: - From the following data obtained at 20 o C shows that the decomposition of
hydrogen peroxide in aqueous solution is a first order.

Time (min) 0 5 10 20

KMnO 4 46.1 37.1 29.8 19.6

ml
min

The values of k are similar and of the same magnitude.

This shows that the reaction conforms to first order equation.

Question 2: The following data in the hydrolysis of acetate at 25 o C in the presence of 0.35 N
HCl used as catalyst produces the following data,

Time ( min ) 0 1200 4500 7.40 ∞

Alkaline ( ml 24.36 25.85 29.32 31.72 47.15

)

From the above data shows that the hydrolysis of acetate is first order.

Let Vo  titre value at time t  0 and V  titre value at time t   , therefore

V  Vo  a & V  Vt  a  x , Vt  Vo  x ,

2.303  V  Vo 
k log  
t  V  Vt 

 V  Vo 
The rate constant is obtained from the slope of the plot of log    versus t which gives
 V  Vt 
2.303
a slope  .
k
Theoretical treatment of Reaction Rates

Collision theory: - The application of the simple kinetic theory of gases to the rate of the bio
molecular process:

A  B  Product , is based on the reasonable assumption that for the reaction to take place;

(a) Molecules A & B must collide

(b) The energy of the colliding molecules must be at least equal to the activation energy (
E ) or Ea

The rate of the reaction is therefore equal to the number of effective collisions per second in
unit volume of the reacting gas.
E

3 1
Total number of effective collision / cm s e RT
. If the concentration of A & B are n A & n B
molecules / cm 3 respectively, then, total number of collision / cm 3 s 1  Zn A n B . Where Z the
collision number is equal to the collision frequency when the concentration of A & B are one
molecule / cm 3 . Since reaction rate  number of effective collisions / cm 3s 1 ,
 E

Rate  Zn A n B e RT
.

Rate  knAnB molecule / cm 3s 1

E

Therefore, k  Ze RT

According to the simple collision theory, the A factor of the Arrhenius equation for
biomolecular reaction is equal to the collision number Z which can be calculated from kinetic
theory expression. Z and A , are compared for a number of reactions and good agreements
observed for reactions involving simple molecules suggest that conditions (a) and (b) are
sufficient in these cases. For reactions between larger molecules where A is less than Z , it
appears that the additional condition (c) must also be satisfied, (c) the molecules must be
suitably oriented on collision this condition can be taken into account by the introduction of a
A
steric or probability factor P into the equation such that k   1 .
Z
The Transition state theory

This approach treats the reaction in terms of equilibrium between reactants A & B and the
transition state complex AB at the top of the potential energy barrier.

The difference in the potential energy of the reactants and the complex is defined as the
activation energy of the reaction. If reaction must take place between A & B , the interacting
molecules must acquire activation energy E a and form a transition complex which can then
decomposed, either to yield the products of the reaction or to reproduce the reactants.

The transition state theory treats the activated complex as a molecular entity with definite
thermodynamic properties. It proposes that it is the concentration of this transition complex,
and more particularly the rate of its breakdown, that determines the rate of the reaction. The
overall reaction can thus be represented as follows: A  B  AB  P  Q , # denotes
transition state quantity. E a  H  RT .
Factors Determining the Rate of Reaction

Nature of the reactant: - surface area of the reactant affects the rate of reaction. Faster in
powdered form than in granular form.

Concentration of the reacting molecules: - increase in the concentration of the reactant

increase the rate of the reaction. Because collision is increased leading to increase in rate. Not
all collisions are effective. Only those molecules which have a certain minimum energy
(activation energy) to overcome the repulsive forces generated by the electron clouds of the
reactants are able to form the product.

Temperature: - An increase in temperature result in an increase in rate because at higher

temperature, the kinetic energy of the reactant increase making their collision more violent &
therefore more probable to cause reaction.

Increase in temperature also alter the distribution of molecular energy to the extent that one
molecule acquire higher kinetic energy. At higher temperature the energies of molecules are
distributed and more molecules acquire more kinetic energies greater than activation energy
leading to increase in the rate of reaction.
Ea

Arrhenius equation shows the temperature dependence of rate of reactions as k  Ae . WhereRT

k  rate constant, A  frequency factor concerned with the number of collisions per unit time,
and the orientation of the reacting species during collision, E a  Activation energy, R =
Universal gas constant and T = Temperature in kelvin.
 Ea
ln k  ln A 
RT

Ea
log k  log A 
2.303RT

1
If rates are studied at different temperatures and log k is plotted against , a straight line is
T
Ea
obtained with slope   . From the slope E a can be easily determined. Alternatively
2.303R
studying rate of reactions at two temperatures T1T2 can also enable us to calculate, E a thus-

Ea
log k1  log A  ............................................................ (1)
2.303RT1

Ea
log k 2  log A  ............................................................ (2)
2.303RT2

Subtracting (2) from (1)

k  Ea  1 1
log  1     
 k2  2.303R  T2 T1 

k  E a  T1  T2 
log 1    
 k2  2.303R  T2 T1 

Enthalpy of activation complex can be calculated from E a  H   RT .

Catalysis
A catalyst increases the rate of chemical reaction. The addition of a catalyst does not change
the stoichiometry of the reaction like in: A  B  C  D Otherwise the reaction would not be
the same one. The catalysed reaction may be represented by:
A  B  Catalyst  C  D  Catalyst . From which it follows that:

(a) The catalyst remains chemically unchanged at the end of the reaction

(b) A catalyst does not alter the position of chemical equilibrium but accelerates the
approach to chemical equilibrium by equally affecting the forward and reverse rates

(c) A small amount of catalyst will promote a large amount of chemical change

Examples: -

(1) 2KClO 3 MnO

2  2KCl  3O 2

(2) 2H 2  O 2 
Pt
2H 2 O

H
(3) CH 3 COCH3  Br2  CH 3 COCH 2 Br  HBr
Many reactions in biological systems are catalysed by enzymes.

Two broad types of catalysis are recognized depending on the kinetic classification of reaction
types. They are:

Homogeneous catalysis: - This is when all the reactants are in the same phase ( gases, liquids
and solids) with catalyst. Example 3 is a representation of this type.

Heterogeneous catalysis: - This is when all the reactants including the catalyst are not in the
same phase. The catalyst constitutes an additional phase as in example 2.
General Acid or Base Catalysis

Many reaction catalysed by acid are also catalysed by many substance which are acid or the
Bronsted acid (proton donor). This is general acid catalysis. Similarly for general base catalysis
not only OH  but also Bronsted base (proton acceptor) can act as base catalyst.
K  K o  K acid C acid  K base C base . Where K is the specific rate constant for overall reaction,
K o is the specific rate constant for non-catalysed reaction, such as occurs in neutral solution,
K acid & K base are catalyst coefficient of acid and bases and C acid & C base are the concentration
of the reacting species.
Mechanism of Catalyst in Acid – Base Catalyst

Addition to or removal of a proton is involved generally, for example in muta - krotation of

GH + H3O+ HG+H + H2 O HG + H3 O+
  glucose Intermediate  - glucose
glucose,

Hydrolysis of ester by mineral acids;

O O H

H3C C + H3O+ CH3 C O+ + H2 O

CH3
O CH3

O-
OH
H3C O
H3 C C O+
C
CH3 + CH3
O+ H
+
O
H H
H
H

O
+
H 3 O+
H3 C C OH
Enzyme Catalysis

Catalysis of chemical reaction in living organism by enzymes of biological origin are extremely
specific e.g. hydrolysis of starch 2C 6 H 10 O 5 n  nH 2 O Diatase
 nC12 H 22 O11 (i.e. starch
converted to maltose sugar)

and C 6 H 12 O 6 Zymase
 2C 2 H 5 OH  2CO 2 .

In general enzyme are divided into 2 classes

(1) Hydrolytic enzyme: - This is a complex acid but a catalyst that accelerates ionic
reaction by the transfer of H  .

(2) Oxidation or Reduction enzyme: - This catalyst is electron transfer.

Mechanism of Catalyst Reaction

Mainly Michaelis and Menten mechanism or scheme explain this mechanism as written below,


k1
E  S  ES * 
k3
EP
k2

Vmax S
Vo 
K m  S

Where K m is the Michaelis-Menten constant, S = substrate and Vo is the initial rate.

Theories of Catalytic Reaction

Intermediate compound formation Theory:- A catalyst enters into chemical combination

with one or more of the reactant forming an intermediate compound which react with some
other reactant to form the product and regenerating the catalyst as in the Michaels-Menton
equation above,

A  B  AB uncatalysed 
A  C  AC* catalysed 
AC*  B  AB  C

The catalyst through its intermediate provides a pathway of lower energy thereby accelerating
the reaction.

Adsorption or surface Theories: - Usually catalyst is solid and the reactant is gaseous or
liquid and the reaction is heterogeneous. Langmuir suggested that action depends on adsorption
of reactant on solid catalyst the adsorbed molecule is then activated probably by weakling the
reactant bonds in it through adsorption. The activated adsorbed molecule then decomposes to
product. Steps involved are as follows;

1. Diffusion of reactant to surface

2. Adsorption of reactant at surface

3. Chemical reaction at surface

4. Desorption of product
Transition State Picture of Catalysis

According to the transition theory, the presence of a catalyst introduces a new reaction pathway
with a lower E a leading to an increase in the reaction rate.

E a1 is the activation energy without catalyst while E a 2 is the activation energy with catalyst.

Activated complex of uncatalyse reaction

Activated complex of catalysed reaction

E a1 Uncatalysed

Potential energy
E a 2Catalysed

Reactant
Product

Reaction coordinate

Since E a 2  E a1 , the reaction in the presence of catalyst proceeds faster than in its absence. At
the molecular level, the presence of catalyst usually introduces additional reaction intermediate
(with a different activation energy barrier) which are reactive enough to decompose to products
in faster step. Example is in acid catalysed bromination of acetone.

 
CH 3 COCH3  H   CH 3 C OH  CH 3  CH 3 COH CH 2
CH 3 COH CH 2  Br2  CH 3 C  OH CH 2 Br  CH 3 COCH 2 Br  H 
For a reversible reaction, the presence of catalyst does not affect the entropy of reaction. It does
not alter position of equilibrium but rather fasten the rate with which equilibrium is attained
since both forward and backward reactions go through the same transition state (principle of
reversibility).

Equilibrium

A reversible reaction is one which proceeds in both forward and backward direction i.e.

A  B  C  D , (where k f & k r are the equilibrium constant for both forward and backward
reaction respectively). Equilibrium is achieved when the forward rate is equal to reverse rate
and in such case, the concentration of A, B, C & D are constants. Supply of reactants in both
directions is constantly reviewed so that equilibrium is dynamic. The position of equilibrium
is measured by equilibrium constant K .

Examples:

H2 + I2 2HI
N2 + 3H2 2NH3

RCOOH + R'OH RCOOR' + H2O

.
Microscopic Reversibility: - when reaction follow same path in forward & backward direction
through the same intermediate, the supply of reactants in both directions is never exhausted.
Therefore the equilibrium is a dynamic one. The extent to which reaction goes is measured by
the equilibrium constant ‘ K ’. From equation (1) A + B  C + D, K is defined as

K
CD .............................................................................. (2)
AB
Generalized equation, aA  bB  cC  dD

K
C D ....................................................................... (3)
c d

A a Bb
The dynamic nature of equilibrium can be illustrated as follows: - assuming that mechanism of
both forward & backward reaction involve single elementary steps, then

d A 
Forward rate =   k f A B
dt

d C
Reverse rate =   k r CD
dt
At equilibrium both rates are equal

k f A B  k r CD
CD  k f K
AB k r
This relationship holds whether the reaction is simple elementary step or complicated. When
K  1 equilibrium lies to the right and when K  1 equilibrium lies to the left.

Measurement of Equilibrium constant ( K ) under Standard Condition

At 25 o C and 1 atm pressure, the equilibrium constant is written as K o and is related to the
standard free energy change as follows, G o  RT ln K o  2.303RT log K o .

G o also measures the position of equilibrium.

G o  ve, K o  1, and equilibrium lies to the right.

Unit of K eq

(1) For reactions in solution, K eq is expressed in terms of concentration

(2) For gaseous reaction ( moldm 3 ), partial pressure ( Nm 2 , mmHg )

N 2 g   3H 2 g   2 NH 3 g 

K eq 
NH 3 
2


moldm 3  moldm 3
 mol  2 dm 6
N 2 H 2 3 
moldm 3  moldm 
3 3

pNH 3 2 Nm 2  Nm 2
K eq    N 2 m 4
pN 2 pH 2 3 Nm 2

 Nm 
2 3

Le Chatelier Principle

Effect of a stress on equilibrium such as (a) change in concentration (b) pressure (c)
temperature can be predicted by applying Le Chatelier principle. Le Chatelier Principle states
that ‘A system in equilibrium react to any change in its conditions in a manner that would tend
to abolish this change’. Let us apply this principle to hypothetical examples:
 Exothermic
A + 3B 2C + D
Endothermic

1 mole 3 moles 2 moles 1 mole

1 volume 3 volume 2 volume 1 volume
4 volume 3 volume

Change of Pressure: - If in a system in equilibrium, the pressure is raised, then Le Chatelier

principle predicts that the system will respond to this external change as to oppose its effect i.e.
the position of equilibrium will alter by promoting that reaction which results in lower pressure
because it proceeds with a reduction in volume. So in this case a higher pressure will cause a
shift in the position of equilibrium from left to right and lead to a higher proportion of C & D
in the reaction mixture. Lowering the pressure of the system will have opposite effect.

Change in Temperature: - By similar reasoning, if the system is in equilibrium and the

temperature is raised, this change will be opposed by promoting the reaction which proceeds
with the absorption of heat i.e. Endothermic reaction, causing a shift in the position of the
equilibrium to the left thereby increasing the proportion of A & B .

Change in Concentration: - Partial or complete removal of D from the equilibrium mixture

will upset the system in equilibrium. Le Chatelier principle predicts that the consequence of
such a change will be a shift in the position of equilibrium to the right with production of more
C & D thereby opposing the reduction in the concentration of D that has been made.
Examples:

Examples high pressure and low temperature

Exothermic
N2 + 3H2 2NH3
Endothermic

High pressure, low temperature and large excess of oxygen

Exothermic
2SO2 + O2 2SO3
Endothermic
Alternating pressure has no effect and high temperature leads to the formation of NO
Endothermic
N2 + O2 2NO
Exothermic
Alternating pressure has no effect and low temperature leads to the formation of CO2 & H2
Exothermic
CO + H2O CO2 + H2
Endothermic
Questions

1. The rate of hydrolysis of isobutane in an acidic aqueous solution is given by

 d Isobutane 
 k Isobutane and the value of rate constant is k  2.2  10 4 s 1 at 25
dt
o
C (i) What is the half-life of the reaction (ii) How long will it take for the
concentration of isobutane to decrease to 0.1% of its initial value at 25 o C (iii) If the
concentration of isobutane in the solution 1.00  10 4 M after the reaction has proceeded
for 3600 seconds at this temperature. What was its concentration when the reaction
began?

2. A substance decomposes according to first order rate law with half-life of 40min. What
fraction of the sample remains after 100min of the reaction
Answer 1

0.693 0.693
t1   4
 3150 s
2
k 2.2  10
 a 
kt  2.303 log 
a  x
 100 
2.2  10  4 t  2.303 log 
 0.1 
2.303  3
t 4
 31404.5s
2.2  10
 a 
kt  2.303 log 
a  x
 a 
2.2  10  4  3600  2.303 log 4 
 1. 00  10 
a  2.207  1.0  10  4  2.207  10  4 M
Answer 2

0.693 0.693
t1    1.73  10  2 s 1
2
k 40
 a 
kt  2.303 log  
a  x
2  a 
1.73  10  00  2.303 log  
a  x
 a 
log    0.752
a  x
a 56

a  x 10
ax 5 1
  0.178 
a 28 5 .6