Paper

Subject:
Physical Chemistry
Topic:
Open Book Test

Submitted To:
Sir Abdul Hamid
Submitted By:
Syed Adnan Bukhari
F19-BS CHEM-1029
BS Chemistry 3rd (M)
 Open Book Test

(I). Write a brief summary of chemical equilibrium (maximum 2000 words).

Introduction:

“Chemical equilibrium represents a state of reversible reaction in which both forward

and reverse reactions are occurring at equal rates all the times.”

Many reactions do not go to completion even if good conditions are preserved.

Reactions proceed to some extent and then deceptively stop leaving considerable quantities of
unreacted materials. When this stage is reached that no extra reaction is apparent, it is said to
have accomplished a state of equilibrium at that temperature and the noticeable properties of
the system do not change with time.

It is obvious that the reaction can proceed in either way and the arrangement of the
system at equilibrium is motionless and stationary. At the equilibrium state the reaction
continues in both directions at equal rates so that the rate of formation of the products is
exactly equal to the rate of disappearance of the reactants.

Characteristics:

Chemical equilibrium has following attributes;

 No apparent change occur

 Dynamic in nature
 Readjust itself when factors are removed
 Catalyst has no effect
 Concentration remain same
 Can be attained from either side
 Maximum stability
 Minimum free energy
 Spontaneous
 Energy loss is low
 In gas phase it is achieved in closed system
 In other phases it is achieved easily
 Reactants and products may equal in number of moles.
Types:

 Physical equilibrium
 Only change in Physical state of reactants
 No other change is occurring
 Chemical equilibrium
 Only change occur in chemical composition
 Homogenous equilibrium
 Only 1 phase exist
 Such as either gas, liquid, solid all reactants are only in 1 phase
 Heterogeneous equilibrium
 More than one phase exists
 Such as solid and liquid or liquid and gas phases exists etc.
 Dynamic equilibrium
 Apparently looks that there is no change but reactions are
occurring on both sides
 Reactants and products are in equal concentrations

Law of Mass Action:

This law was first articulated by C.M. Guldberg and P. Waage in 1864 and helps us
to find the relations between the concentrations of reactants and products at equilibrium in the
reactions.

“The law states that at persistent temperature, the rate of a chemical reaction is
proportional to the active masses of reacting substances.”

For supposed reaction values of Kc & Kp are;

xA+yB mC+nD

Kf= [A][B]

Kr=[C][D]

Kc= Kf/Kr
 Kc= Kf/Kr

Kc=([C]m[D]n)/([A]x[B]y)

Kp= (PCm . PDn)/ (PAx . PBy)

And the relationship between Kc & Kp is;

kp = kc(RT)np-nr

Units:

Kc & Kp may have different values and units but their formula of derivation of units are
general.

For Kc

 Kc=(MolL-1)np-nr

And for kp

 Kp=(atm-1)np-nr

Example:

H 2 + I2 2HI (Kc = 57)

Kc = [HI]2 / ([H][I])

Kp = p(HI) / p(H) p(I)

Kp = Kc (RT)np-nr

Kp = Kc (RT)2-1-1

Kp = Kc (RT)2-1-1

Kp = Kc (RT)0

Kp = Kc (1)

Kc = Kp

{So, Kc = Kp when np-nr = 0 and RT = 1}

Applications of Kc:

1-Extent of Reaction:

Kc helps us to find out the extents of reactions by comparing Kc values with

the factors. There are 3 different occasions designed for the extent of reaction.

 Kc > 103
When Kc value is very larger than a lot of products are there
and doesn’t need to attain equilibrium or end.
H2 + O 2 2H2O (Kc = 2.4 x 1047)
 Kc (Not larger Not smaller)

At this stage both reactants and products will be in equal

concentrations
H 2 + I2 2HI (Kc = 57)
 Kc < 10-7

When Kc value is very small than a lot of reactants are there and
need to attain equilibrium or end.(Means formation of products will
occur)

N2 + O 2 2NO (Kc = 4.8 x 10-3)

2-Direction of Reaction:

Kc helps us to find out the direction of reactions by compairing Kc values with

the Qc. There are 3 different occasions designed for the extent of reaction.

aA + bB cC + dD

For this equation ;

Kc=([C]c[D]d)/([A]a[B]b) [At Equilibrium]

Qc=([C]c[D]d)/([A]a[B]b) [At time "t"]

 e.g:

H 2 + I2 2HI (Kc = 57)

For this reaction both constants have diffent values and we can determine
direction of rection by compairing them as such:

 Kc = 57
 Qc = 8

Their cases are 3 upon which relational direction can be predicted;

 Kc >Qc
Reaction will proceed in forward direction
Because reactants are greater in number
 Kc =Qc

Reaction will be in equilibrium

Because reactants and products are equal in number

 Kc <Qc

Reaction will proceed in reverse direction

Because products are greater in number

Difference between Kc and Qc:

Kc Qc

Reaction Constant Reaction quotient

Find out in equilibrium Find out at any time except equilibrium

Constant at all conditions Constant at specific STP and may vary

with temperature and other factors.

For HI production its value is; For HI production its value is;
Kc = 57 Qc = 8
Le Chatelier’s Principle:

A French Chemist Henry Le Chatelier (1884) studied the effect of concentration,

temperature and pressure on a large number of systems in equilibrium. He summed up his
conclusions in the form of a generalization, known as Le Chatelier's principle. This principle
is general one and is applicable to all physical and chemical equilibrium.

According to this principle,

"If a system at equilibrium is disturbed by changing the variables such as

temperature, pressure or concentration, then the system will tend to adjust itself so as to
minimize the effect of that change as far as possible."

Applications:

1. Synthesis of Ammonia

Synthesis of amrita is of great importance in manufacturing as it in used for

the manufacture of nitrogen fertilizers such as urea, amonium nitrate etc. In the
synthesis of amnia by Haber's penes established of nitrogen and hydreogen in the ratio
of 1: 3 by volume is paned through an ion coil lined inside with superbly divided iron
maintained at constant temperature (450).

Ammonia is formed as shown in equation

N2 + 3H2 2NH3 H= -93.47 KJ/mol

When time is “t”

 Nitrogen = (1-α) / V
 Hydrogen = (3-3 α) / V
 Ammonia = (2α) / V

At equilibrium their concentrations are

 Nitrogen = 1
 Hydrogen = 3
 Ammonia = 2
Kc = (4 α2V2) / (27{1- α })
Effect of P/V:

Increased P------------------ Forward

Decreased p------------------Forward

Change in Concentration:

Increased V------------------ Backward

Decreased P------------------Backward

Effect of Temperature:

Increased Product------------------ Backward

Decreased Product------------------Forward

Increased Reactants------------------ Forward

Decreased Reactants------------------Backward

Formation of NO (Nitrogen Oxide)

Formation of NO (Nitrogen Oxide)is a reversible chemical reaction and we will

discuss its factors and effects to study Le Chatelier’s Principle.

N2 + O 2 2NO

Effect of P/V

As np-nr is zero there will be no effect of pressure on reaction because volume

change has no effect on equation.

Change in Concentration

When products are less and reactants are greater then reaction will be move in
forward direction and vice versa.

Effect of Temperature

When we increase the temperature reaction goes in forward direction and vice versa.
Calculation Of α From Density Measurement

Phosphorus pentachloride is the chemical complex with a formula of PCl₅. It is one of

the most vital phosphorus chlorides, others being PCl₃ and POCl₃. PCl₅ finds use as a
chlorinating reagent. It is formed by PCl₃ and Cl 2 . Alpha can be derived by studding its
formational process;

PCl5 PCl3 + Cl2

When time is at its initial position or t=0

1 0 0

At equilibrium

1-α/v α/v α/v

Let;

Vapour density before dissociation = D

Vapour density after dissociation = d

Volume occupied by 1 mole of PCl3 = V

Volume occupied by 1+ α mole of PCl3 = (1+ α )V

D∝ 1/V

So , D=constant 1/V

d∝ 1/V(1+ α )

So , d=constant 1/V(1+ α )

D/d= {constant 1/V} / { constant 1/V(1+ α )}

So,

α = D/d -1

it means when d is at equilibrium D will be t=0

Homogeneous Equilibrium In liquid System:

CH3COOC 2H5 + H 2O CH3COOH C 2H5OH

When time is at its initial position or t=0

α/v b/v 0 0

At equilibrium

α-x/v b-x/v x/v x/v

kc = ([CH3COOH][C2H5OH]) / ([H2O][CH3COOC2H5])

kc = x2 / (a-x)(b-x)

kc is independent of volume, if phase is either gaseous or liquid if change in n=0

Heterogeneous Equilibrium:

CaCO3 CaO + CO2

ka = { aCaO . aCO2 } / { aCaCO3 }

o If activity of pure solid or pure liquid is 1 than aCaCO3 =1

o And when activity is 1 and pressure is not high then ka = aCO2

o If gas is behaving ideally then a=P and ka =PCO2

Density capacities are a reliable way to check the purity of diluents (raw, middle, or
final products) in various industries such as chemical, pharmacological, petrochemical,
cosmetic, and individual care.

The densitometer can be used to check the purity of solvents. To ensure accurate,
comparable results, the measured density (d) – obtained at the dimension temperature – must
be remunerated to a orientation temperature. Recompense of results to a reference
temperature entails facts of the alpha (α) coefficient for each solvent.

Relation between ∆G and Equation Constant:

∆G is the variation of Gibbs (free) energy for a organization and ∆G° is the Gibbs
energy variation for a system under usual conditions (1 atm, and 298K). Where ∆G is the
difference in the energy between reactants and products. In addition ∆G is genuine by
external features that variation the kinetics of the reaction.

Relation between ∆G and Equation Constant can be derived as;

aA + bB cC + dD

G = G2 - G1

G =nRT ln P2 / P1

G=Go + RT ln P2/1

G=Go + RT ln P

aA= aGA= aGoA + RT ln PA

bB= bGb= bGob + RT ln Pb

cC= cGc= cGoc + RT ln Pc

dD= dGd= dGod + RT ln Pd

G =∑G(P) - ∑GR

G= G + RT ln [C]c[D]d / [A]a[B]b

At equilibrium;

when G =0 then

0= G + RT ln [C]c[D]d / [A]a[B]b

G =- RT ln kp
 When G is 0 then there will be equilibrium and if G is with positive reaction

will be non-spontaneous and if G is with negative sign reaction will be spontaneous.

Vant’s Hoff Equation:

In 1884, Dutch chemist Jacob Hendricks proposed Vant’s Hoff Equation. It is

quantitative study of effect of temperature on K. The van 't Hoff equation has been generally
utilized to discover the changes in state functions in a thermodynamic system. The van 't Hoff
plot, which is derivative from this equation, is especially operative in valuing the
transformation in enthalpy, or total energy, and entropy, or number of accessible microstates,
of a chemical reaction.

It states that:

“Change in equilibrium constant K of chemical reaction to the change in temperature

T, give the standard enthalpy change H for the process.”

Go = Ho - TS

Go = _RT ln K

Go = Ho - TS

ln K ={ - Ho / RT } + { S/R }

For exothermic reaction - Ho so temperature will decrease K and endothermic reaction +

Ho so temperature will increase K.

For different temperature Vant’s Hoff equation will be different such as;

 ln K1 ={ - Ho / RT } + { S/R }
1

 ln K2 ={ - Ho / RT } + { S/R }
2
 Converting ln to log10

 ln K2/K1={ - Ho / 2.303R } + { T -T / T T } [where R=8.314]

2 1 2 1

(II). Prepare 30 authentic MCQs related to chemical kinetics with answer key.

The rate constant of 0 order reactions has the unit

i. s-1
ii. mol L-1 s-1
iii. L2 mol-2 s-1
iv. L mol-1 s-1
When the rate of the reaction is equal to the rate constant, the order of the reaction is
i. 0 order
ii. first order
iii. second order
iv. third order
In the Haber process for the production of ammonia the following catalyst is used
i. Platinized asbestos
ii. Iron with molybdenum
iii. Copper oxide
iv. Alumina
A substance ‘A’ rots by a first-order reaction starting originally with [A] = 2.00M and after
200min, [A] becomes 0.15M. For this reaction t1/2 is
i. 53.72 min
ii. 50.49 min
iii. 48.45 min
iv. 46.45 min
The rate of a chemical reaction states:
i. the reactants taking part in the reaction
ii. the products formed in the reaction
iii. how slow or fast the reaction is taking place
iv. none of the above
In the reaction 2A + B → A2B, if the concentration of A is doubled and that of B is halved,
then the rate of the reaction will
i. increase 2 times
ii. increase 4 times
iii. decrease 2 times
iv. remain the same
The average rate and instantaneous rate of a reaction are equal
i. at the start
ii. at the end
iii. in the middle
iv. when two rates have a time interval equal to zero
Example of chemical method to find out Rate of reaction is----------?
i. Conductivity
ii. Optical rotation
iii. Gravimetric Technique
iv. Resonance
When qc =kc then--------?
i. Reaction is forward
ii. Reaction is reverse
iii. At equilibrium
iv. Ror does not change
Value of kc for the production of HCl is ----?
i. 57
ii. 4x103
iii. 5.4x103
iv. 67
Le Chatelier's principle states that
i. if a chemical system at equilibrium is stressed, the system will adjust to increase the
stress
ii. if a chemical system at equilibrium is stressed, the system will adjust to reduce
the stress
iii. if a chemical system at equilibrium is stressed, the system will not adjust
iv. all of the above
0.004 M Na2S04 aqueous solution is isotonic with 0.01 M glucose solution at 300 K. Thus,
degree of dissociation of Na2S04 is
i. 50 %
ii. 25 %
iii. 75 %
iv. 100 %

Half-life of first order reaction is

i. Greater
ii. Lesse
iii. Higher
iv. Constant

Order of reaction can be identified by plotting graphs of

i. reaction only
ii. concentration only
iii. pH value
iv. reaction and concentration
For the first and second order of reactions the graph will be
i. straight line
ii. falling
iii. rising
iv. curve
The time compulsory for the concentration of reactant to fall down to its half value from the
original value is
i. reaction life
ii. half life
iii. reactant
iv. ROR
For a chemical reaction A→B, it is found that the rate of reaction duos when the
concentration of A is increased 4 times. The order of reaction is
Two
i. One
ii. Half
iii. Zero
What will be the fraction of molecules having energy equal to or greater than activation
energy, Ea?
i. K
ii. A
iii. Ae-Ea/Rt
iv. e-Ea/Rt
For a first order reaction (A) → products the concentration of A changes from 0.1M to 0.025
M in 40minutes.
i. 3.47 × 10–4 M/min
ii. 8.47 × 10–4 M/min
iii. 5.47 × 10–4 M/min
iv. 2.47 × 10–4 M/min
The activation energy of a reaction at a given temperature is found to be 2.303 RT J mol–1.
The ratio of rate constant to the Arrhenius factor is;
i. 0.001
ii. 0.5
iii. 0.6
iv. 1
The time required for 100% completion of a zero order reaction is
i. a/K
ii. 2a
iii. 2a/k
iv. K/3a
The rate of a chemical reaction doubles for every 10°C rise of temperature. If the temperature
is raised by 50°C, the rate of the reaction increases by about
i. 32 times
ii. 10 times
iii. 22 times
iv. 2 times
Which of these changes with time for a first-order reaction?
i. Rate of reaction
ii. Rate constant
iii. Half-life
iv. All of these
Based on the above data which one of the following is correct?
i. rate = k[A] [B]2
ii. rate = k[A]3 [B]
iii. rate = k[A] [B]3
iv. rate = k[A] [B]
The rate of reaction
i. Increases as the reaction proceeds
ii. Decreases as the reaction proceeds
iii. Remains the same as the reaction proceeds
iv. May decrease or increase as the reaction proceeds
On increasing the temperature the rate of reaction increases mainly because
i. The activation energy of the reaction increases
ii. Concentration of the reacting molecules increases
iii. Collision frequency increases
iv. None of these
Spontaneous reactions are
i. Moderate
ii. Slow
iii. Fast
iv. not natural
Unit of rate of reaction is
i. Moles dm-3 sec-1
ii. Moles dm-3
iii. Moles sec-1
iv. Mol-1 dm3 sec-1

The value of activation energy is primarily determined by

i. Temperature
ii. Effective collision
iii. Concentration of reactant
iv. Chemical nature of reactants and products
What are the units of k for the rate law: Rate = k[A][B]2, when the concentration unit is
mol/L?
i. s-1
ii. s
iii. L mol-1 s-1
iv. L2 mol-2 s-1