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CHAPTER-11

THERMOCHEMISTRY
Definition:
The branch of chemistry which deals with the heat evolved or absorbed during a

chemical reaction is called Thermochemistry.

Or

Each and every physicochemical change is accompanied by some new changes in

which evaluation or absorption of heat occur that will be called Thermochemistry.

Example of Thermochemistry:
1. All those reaction in which heat evolution or absorption occur are the

examples of Thermochemistry.
2. On the basis of heat evolved or absorbed, there are two types of reactions.
3. Exothermic reaction.
4. Endothermic reaction.

Exothermic Reaction:
Those reactions in which the evolution of heat occur is cld exothermic reaction.

For Example: When CaCO3 is dissolved in water, it evolves heat which is an

example of exothermic reaction and we can say that it is Thermochemistry.

i.e. CaCO3 CaO+CO2+H

Endothermic Reaction:
Those reactions in which the absorbtion of heat occur is called endothermic reaction.

For Example: When KNO3 is dissolved in water it heat from the surrounding which

is an example of endothermic reaction.

Other Examples of Endothermic Reactions:


1. Decomposition of KT.

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2. Decomposition of KNO3

Note:
Chemical change is nothing but the breaking of old bonds and formation of new

bonds.

Energy Change in Chemical Reaction:


It can be explain as;

1. Thermochemical Equation:
That equation which shows;

a. Nature of reactants and products.


b. Physical state of reactants and products.
c. Enthalphy Changes of reaction
d. is called thermochemical equation.

Energy Changes:
During a chemical reaction heat must be evolved or absorbed.

i.e. A + B C+ D H= +

MCQs:
Heat evolved or absorbed during a chemical depends upon;

a. Number of bonds formed.

b. Number of bonds broken.

c. Strength of bonds.

If H= + ve:
It means that;

1. Strong bonds are broken and weak bonds are formed.

A A + B B A B + A B H= +
Strong bond weak bond

2. Reaction is endothermic.

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3. The energy of reactant is less than the energy of the products.

4. Product is less stable.

5. Activation energy of forward reaction is greater.

6. Reactants are stable.

If H= - ve:
It means that;

1. Weak bonds are broken and strong bonds are formed.

2. Reaction is exothermic.

3. Energy of reactant is greater than the energy of product.

4. Products are more stable.

5. Reactants are unstable.

Reaction:
A ABB AB AB
Weak bond strong bonds formed

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Difference between Spontaneous and non- Spontaneous process
Spontaneous NON- Spontaneous

i. Definition: i. Definition:

That process which do not require an that process which required a specific

external assistant or energy for operation assistant for operation.

is called spount anas rn

ii. Natural Tendency ii. Natural Tendency

It has natural tendency to occur. It has no natural tendency to occur.

iii. Unidirectional iii. Bidirectional

It is unidirectional in nature. It is bidirectional in nature.

iv. Non Equilibrium iv. Equilibrium

It goes from non equilibrium state to It goes from equilibrium state to non

equilibrium state. equilibrium state.

v. Irreversible. v. Reversible.

It is irreversible process. It is reversible process.

vi. Real Process. vi. Un-Real Process

It is real process in nature. It is unreal process.

vii. Unstable. vii. Stable.

It goes from unstable state to stable state. It goes from stable state to unstable state.

i.e. water from low potential to high

potential.

viii. Gips free Energy. viii. Gips free Energy.

G should be negative, The useful part It should be positive for non-spontaneous

of the energy is called Gips free energy. reaction.

G = +ve

ix. Enthalpy. ix. Enthalpy.


The enthalpy of a spontaneous reaction

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should be negative. The H of non-spontaneous reaction is
positive.
H + (-) negative.
H = (+) positive.

x. Entrophy. x. Entrophy.

It should be positive. It should be taken negative.

S = + ve S = - ve

xi. Energy of product. xi. Energy of product.

The energy of the product is low. The energy of the product in non-

spontaneous reaction is always high.

xii. Examples. xii. Examples.

It has the following examples. It has the following examples.

xiii. Evaporation. xii. Bond Breaking.

It is an example of spontaneous process It is an example of non-spontaneous

but evaporation is endothermic process. process and is Endothermic. It is mostly

endothermic.
Note: soutanes process are mostly

exothermic except evaporation

xiv. Melting of ice xiv. Freezing of water .

Melting of Ice is spontaneous process. Freezing of water is non-spontaneous

process.

xv. Cooling of Hot Tea. xv. Heating of cool tea.

xvi. Note. xvi. Note.

Escape of steam from pressure cooker Decomposition of water by electrolysis is

when the safety value of the cooker is non spontaneous process.

opened is spontaneous process.

xvii. Flow of water from high xvii. Leftning of water from


potential to low potential is lower to higher potential is
spontaneous. no spontaneous.

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xviii. Burning of natural gas xviii. Compressing of gas by
is spontaneous. applying pressure.
MCQs:
When Zn pieces are dipped into the solution of CuSO4, the blue colour of (CUSO 4)

solution disappear which is an example of spontaneous process.

System:
A substance undergoing a physical or chemical change and is under scientific study is

called system.

Classification:
System has been classified into three types;

1. Open system.

2. Close system.

3. Isolated system.

Open System:
That system from which the free exchange of both matter and energy occur with

surrounding is called open system.

For example:
Boiling of water is open container is an example of open system.

Close System:
That system from which only the exchange of energy occur with the surrounding is

called closed system.

For example:
Tea port.

Isolated System:

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That system from which neither the exchange of matter nor energy occur is called

isolated system.

For example:
Thermoflask.

Surrounding:
Each and every thing around the system is called surrounding.

Or

The environment in which the system is present is called surrounding.

Boundary:
That line which separate system from surrounding is called Boundary.

Bulk Modulus:
Bulk modulus means that not only a single molecule of a system should be

mentioned but all should be mentioned.

Note:
1. It is not necessary to mention or fixed the values of all state function.

2. A state property has definite values in a given state independent of the path

followed.

3. It is not necessary to know all state function.

4. If we know the values of some state function, the values of other can be found

by the help of the following formula;

P1V1 = P2 V2

MCQs:
Heat and work are not state function but thermodynamic function and path function.

State:

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The specific condition of a system is called state.

Explanation:
1. State of a system is described by;

a. Temperature.

b. Volume.

c. Pressure.

d. Internal Energy.

e. Entropy.

2. The state of a system is determined by certain macroscopic properties which

are called state properties.

State Function:
These properties which describe the state of a system is called state variable or state

function.

It is independent of the path followed.

It depends upon.

i. Initial State.

ii. Final State.

Initial State:
The condition of a system before a change occur is called initial state.

For initial state are state properties can be written as;

i.e. Temperature = T1

Pressure = P1

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Volume = V1

FINAL STATE:
Internal Energy:
The total energy contained in a system is called internal energy.

Or

Sum of all possible kinds of energy present in a system is called internal energy.

It is the sum of potential energy and kinetic energy of a system. Or

Explanation:
The internal energy is because of two energy

1. Kinetic Energy.

2. Potential Energy.

Kinetic Energy:
1. The energy produced due to the motion of electron is called Kinetic Energy.

2. Kinetic Energy is produced because of the following motion.

i. Translational Motion.

ii. Vibrational Motion.

iii. Rotational Motion.

Potential Energy:
It is produced due to the position of particles and the position of particles is

because of bonding forces.

The bonding forces are of two types;

i. Intermolecular Forces.

ii. Intramolecular Forces.

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Note:
It is impossible to determine the internal energy of a system but however change in

internal energy can be determined.

Mathematically:
E = E2 E1

Numerical Type

E = Change in internal energy.

Pattern of MCQs Test:


The initial energy of a system was 10kj/mol after heating its internal energy become

15kj/mol. So find change in its energy?

So,

E1 = 10 kj/mol

E2 = 15 kj/mol

So

E = E2 E1

E = 15 10

E = 5kj/mol

Note:
Internal energy is independent of the path i.e. that change has brought by

whatever source i.e heating by coal, petrol or by some other means.

It only depends upon the initial and final state.

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Results of Internal Energy:
1. If internal energy increases the temperature and kinetic energy will be

increases.

2. If the internal energy increases energetic phase occur.

3. Increases in internal energy, a chemical reaction occur.

4. Increase in internal energy, the old bond breaks.

First Law of Thermodynamics:


This law is also called law of conservation of energy because in this law the total

energy remain constant.

Statement:
The total energy of the system and surrounding remain constant.

OR

The energy lost y one system is equal to the energy gained by the surrounding.

Note:
Energy inters or go out from a system in the form of heat or energy.

Explanation:
Let us consider a system;

i. In the initial state its energy is E1.

ii. Now if heat q is added to it then according to first law of thermodynamics it

total energy become.

E2=E1+q (i)

iii. Due to heat the piston is pushed upward against the atmospheric pressure and

since work is done by the system.

So the energy of the system in the final state will be;

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E2=E1+q-W (ii)

W = Work done by the system.

Rearranging

E2=E1+q-W

E = q W (a)

Or

q = E + W (b)

Equation (a) an d(b) are the two form of first law of thermodynamics.

Where;

q = Heat evolved.

W = Work done.

E = Change in energy.

Note:
For small change first law of thermodynamics can be written as;

dE = dq + dW

Special Forms of First Law of Thermodynamics:


Under specific condition the first law of thermodynamics can be written as;

1. Work Done at Fixed Volume:


If heat is given to a system and the piston is fixed then the work done is zero because

the piston do not cover distance in the direction of force.

And the heat given to a system is converted into internal energy only and since the

internal energy of the system increases.

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Since;

According to first law of Thermodynamics.

E = q W

W=0

E = q 0

E = q

Since;

Change in energy is equal to the heat given.

2. If No Heat Enter Or Go Out:


If neither heat enter nor go out from a system then the work is done on the system.

So,

According to First Law of Thermodynamics

E = q W

E = + W q=0

Since this is called adiabatic work.

3. Heat Given to System:


If heat is given to a system then at the same time work is done on system.

E = q +W

4. Heat Go Out from System:


If the heat is given out from a system then the work will be negative.

E = q W

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Sign Convention for Work And Heat:
If;

- ve q = Heat go out from system.

+ ve q = Heat enter to system.

+ ve W = Work done on system.

- ve W = Work done by the system.

Expansion Work (Pressure Volume Work):


Consider a cylinder having movable piston containing gases.

The cross sectional area is A.

The pressure on the piston is given by;

F
P I
A
OR
F PA II

Now if the piston moves upward by a distance l then the work done on the system

will be;

W F l

Now

Putting the values of II in equation III.

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W PAl
Q l. A V
W PV IV
Now from First Law of Ther mod ynaic
E q W V
Q Put the value of W from IV to V
E q PV
E q PV
Q P V W

CONCLUSION: This is called expansion work.

Since from this equation we can calculate

E = ?

q=?

W=?

From First law of Thermodynamics

E q W
E qPV
Q W PV
E q PV

From this equation we can find

q=?

E = ?

W=?

Application of First Law of Thermodynamics:


There are two applications;

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i. Isochoric Process.

ii. Isobaric Process.

i. Isochoric Process:
The heat evolved or absorbed during a chemical process at constant volume is called

isochoric process.

Explanation:
Let us consider a system enclosed in a cylinder having immovable piston or fixed.

Now

If heat is given to a system q then according to first law of thermodynamics.

E q PV
q E PV 1
But the piston is immovable so changein volume is zero.
V 0
So (1) become
q E P (0)
q E 0
Since
qv E

Conclusion:
In isochoric process the internal energy will be very high because the heat given is

converted into internal energy.

Isobaric Process:
The process occur at constant pressure is called Isobaric Process.

The work done under atmospheric pressure that will be called isobaric process.

The process occur in the lab in an open vessel is called isobaric process.

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Explanation:
Let use consider a cylinder having frictionless, weightless and movable piston.

Initial state:
Initially the energy of the system is E1 and the volume of the system is V1.

Since;

Initial volume = V1

Initial Energy = E1

Final State:
Now if heat is given to a system the piston will go upward and the energy of the

system will become E2and the volume become V2 due to which work is done;

Final Energy = E2
Final Volume = V2

Form First Law of Thermodynamics:


Now from first law of thermodynamics we have that;

E q W 1
from pressuer volume work
W PV
So equaiton (1) become as;
E q PV 2
Re arranging equation (2)
q p E PV 3

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But ;
V V2 V1
E E2 E1
Putting the values of " V " and " E " in equation (3)
So
q p ( E2 E1 ) P (V2 V1 )
q p E2 E1 PV2 V1 ) 4
Re arraning eqution (4)
q p ( E2 PV2 ) ( E1 PV1 ) 5

From Enthalyphy Definition:


From the definition of enthalphy we have that;

Enthalphy = Internal Energy + Work

H = E + PV

Since;

Now putting that values in equation (5)

So, equation (5) become as;

q p H 2 H1 6
Q H 2 E2 PV2
H1 E1 PV1
Q H 2 H1 H
So (6) become as;
qp H 7 proved
Now comparing (3) and (7)
H E PV 8

Conclusion:
1. H can be find out experimentally.

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2. H is greater by a factor PV from E.

MCQs:
For liquid and solid

V 0 so
H E
Since
For solid and liquid equation (8)
can be written as;
H E

Standard Enthalphy Change:


The enthalphy change of a substance present in its standard state is called standard

enthalphy change.

Or

The change in enthalphy measured at room temperature and one atmospheric pressure

when the reactants and products are present in their standard stare is called Standard

Enthalphy Change.

Standard State:
The most stable physical state of a substance in which it exist at room temperature

and pressure.

Temperature = T = 298k or 250C


Pressure = P = One atm.

For example:
Most stable physical state of water is liquid state.

Representation:
H298
0

Standard enthalphy change is represented by

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MCQs:
The enthalphy of the element present in their elemental state is arbitrary zero.

i.e Standard enthalphy state of C = zero

Heat Capacity:
The amount of heat absorbed by a system to raise its temperature by one degree is

called heat capacity.

Unit:
Its S.I unit is JK-1/mol

Note:
The molar heat capacity of water is 4.2 kJ/mol

The capacity or ability of a system to absorb heat and store energy is called heat

capacity.

Note:
As the system absorb heat then the (KE) of the particles of the system increases and

since the temperature of the system will be increases.

Expression of Heat Capacity:


Heat capacity has two types

Specific heat capacity.

Molar heat capacity.

Specific Heat Capacity:


It is the amount of heat absorbed by one gram of a substance to raise its temperature

by one degree that will be called specific heat capacity.

T 10 c
1 gram 1 gm
Heat

i.e.

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Unit:
J/ gm.k

Molar Heat Capacity:


It can be defined as The amount of heat required to raised the temperature of one

mole of a substance by one degree is called molar heat capacity.

Unit:
Its unit is KJ/mol

Expression of Molar Heat Capacity:


It can be expressed as;

i. Molar Heat capacity at constant volume.

ii. Molar Heat capacity at constant pressure.

i. Molar Heat Capacity at Constant Volume:


It is the amount of heat required to raise the temperature of one mole of a substance

by one degree at constant volume. It is represented by Cv.

ii. Molar Heat capacity at constant pressure.


It is the amount of heat required to raise the temperature of one mole of a substance

by one degree at constant pressure is called molar heat capacity at constant pressure.

It is represented by Cp.

Hess Law of Constant of Heat SUMMATION:


Back Ground:
This law was presented by G.H Hess in 1840.

Statement:
This law states that the amount of heat evolved or absorbed during a chemical

reaction will be the same, either if the reaction occur in one step or in several steps.

Or

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The heat of reaction depends only on the initial and final state of the system and is

independent of the intermediate steps between reactants and products.

Or

The enthalphy changes of a system depends upon its initial and final state and is

independent of the path followed.

Mathematically:
Hess law can be written as;

H = H1+H2 + H3..Hn

General Verification:
Since the heat evolved from A to D will be the same as that of heat evolved from A to

B and B to C and C to D.

A D (Direct)

A B

A C

C D (Indirect)

So

According to Hess Law

H = H1+ H2 + H3
( A D )

Experimental Verification:
Let us consider the conversion of carbon into CO2. This may occur in two ways;

Direct Method

Indirect Method

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i. Direct Method:
This is one step method.

In this step excess oxygen reacts with carbon to form CO2.

Reaction:
C O2 CO2
(s) (g)
excess

H 393kJ / mol

ii. Indirect Method:


It is two step methods.

First Step

Second Step

a. First Step:
In this step carbon react with limiting oxygen to form carbon monoxide.

Reaction:

C 1 O2 CO
2
lim ited

H1 110kJ / mol

b. Second Step
In this step carbon monoxide is again reacts with limited oxygen to form CO2.

Reaction:

CO 1 O2 CO2
2
lim ited

H 2 282.8 kJ / mol

Conclusion:
Since according to Hess law heat evolved must be the same, so;

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H H1 H 2
393.8 110.8 282.8
393.8 393.8

Conclusion: Since the heat evolved or absorbed is the same in both methods.

Second Example:
Sodium bi-carbonate can be prepared by two methods.

i. Direct Method

ii. Indirect Method

i. Direct Method:
In this method CO2 is reacted with sufficient sodium hydroxide to from Na 2CO3 the

heat evolved is in this step is 89KJ/mol.

Reaction:
2 NaOH CO2 Na2CO3 H 2O
H 89 kJ / mol

ii. Indirect Method:


NaOH CO2 NaHCO3
Limite

H 48.4 kJ / mol

Step II:
In this step CO2 is again reacted with NaOH (limited) and heat evolved is -41kJ/mol.

Reaction:
NaHCO3 NaOH Na 2CO3 H 2O
(lim ited )

Conclusion:

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According to Hess Law the heat evolved or absorbed is the same in both steps.

H H1 H 2
H 48 (41)
89.0 89

Born Haber Cycle:

It is the experimental verification of Hess Law for the calculation of Latie energy of

Binary Ionic Compound, indirectly.

Statement:

That Cycle which is used for the experimental determination of Latice Energy of an

Ionic Crystal is called Born Haber Cycle.

Principle:

It is based on the principle that net energy change during cyclic process will be

zero.

Note:

Born Haber Cycle is the practical application of Hess Law.

Explanation:

Latice energy is the amount of energy when one mole of an ionic compound

is formed from its component in gases from.

NaCl is an ionic compound.

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It can be formed by two methods.

Direct method.

Indirect method.

Direct Method:

In this method NaCl is formed in a single step and the heat evolved is 410.03 kJ/mol.

Na 1 Cl2 NaCl
(s) 2
lim ited

H 410.03 kJ / mol

Indirect Method

In this method NaCl can be prepared in several steps.

Step I (Sublimation):

In this step solid sodium is converted into gaseous form.

Na Na
(s) (g)

H 108.84 kJ / mol
(s)

Step II (Heat of I.P):

In this step the gaseous sodium is converted into gaseous ions. The energy required is

ionization energy i.e.

Na Na 1e
(g)

H 443.7 I .P
(s)

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Step III (Heat of Disassociation):

The conversion chlorine molecule to atomic chlorine.

Disassociation occur. (1) Endothermic

H 242

Step IV (Heat of Electron Affinity):

In this step the chlorine again electron from the sodium.


Cl ie Cl

Step V (Latice Energy):

In this step Na+ react with Cl- to form NaCl.

The energy liberated called lattice energy.

So;

Hf H H H H
(s) ( I .P) ( D) ( E . A)

Note:

Hess Law can be applied to those reactions which are very very fast or slow (very

very slow).

Application:

Hess Law can be used for the determination of the following reactions.

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1. Heat of formation.

2. Heat of combustion.

3. Head of Neutralization.

4. Heat of Reaction.

5. Heat of Solution.

6. Lattice energy of compound.

Heat of Formation:

The amount of heat evolved or absorbed when one mole of a compound is formed

from its element in its standard form is called standard heat of formation.

Hess Law can be used to determined the heat of formation for those reactions which

cannot be determined directly.

Reason:

Because;

i. Such reactions does not occur easily.

ii. Formation of bi-products occur.

iii. Occur very very fast.

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iv. Occur very very slow.

In such cases the reaction is carried out in different steps, and for each steps the heat

is determined and then added with each other by Hess Law;

Application of Hess Law:

The following are the application.

1. Heat of Formation:

The amount of heat evolved or absorbed during a chemical reaction when one mole fo

products is formed.

For Example:
C H 2 CH 4 Hf 74kJ / mol
s g g

C O2 CO2 Hf 393kJ / mol

Note:
2 H 2 O2 2 H 2O VHf ?

This is not the heat of formation because 2 mole of product has been formed, where as

in the light of definition one mole should be formed.

2. Standard Heat of Rxn:

The amount of heat evolved or absorbed in 2 chemical reaction in which the reactants

and products are present in standard form is called heat of rxn.

Mathematically:

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H rxn H H
products reac tan ts

Example:
CaO CO2 CaCO3 H rxn ?
H rxn (H CaCO3 ) (H 0
CO2 )

Heat of Neutralization:
When an acid react with base it is called neutralization.

The quantity of heat evolved when one mole of hydrogen ion from an acid react with

one mole of OH- negative ion from a base to form one mole of H 2O is called heat of

neutralization.

Unit:
Kilo Joul/mol = kJ

Reaction:
H- + OH- H2O H=()

Note:
The heat of neutralization of strong acid with strong base is always constant. Because

in all strong acid and base same reaction occur.

i.e. HCl + NaOH NaCl + H2O

Standard Heat of Combustion:


The amount of heat evolved or absorbed when one mole of a substance is burnt in the

presence of sufficient oxygen is called standard heat of combustion.

Unit:
kJ/mol

Example:

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C + O2 CO2 H = -393.8

Note:
It is both heat of combustion as well as heat of reaction but not heat of formation.

Heat of Solution:
When one mole of a compound is dissolved in sufficient amount of water, so that no

heat is evolved or absorbed on further dilution is called heat of solution.

Unit:
Kilo Joul = kJ

Example:
NH4 Cl = H = + 160kJ/mol

Calorimetric:
Measurement of Enthalphy Changes:
The enthalphy of system can be checked by two methods.

Direct Method

Indirect Method

Direct Calorimetric:
It is used for those rxns which occurs smoothly till completion and cleanly occur.

No bi-product are formed, no side rxn

e.g. combustion and neutralization.

Heat evolved or enthalphy

H = m x s x T

Bomb calorimetry is used for the heat measurement in a rxn.

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Rxn changer is made from glass.

Initial temperature = T1

Final temperature = T2

T = T2 T1

Exothermic Rxn:
The reaction carrying on in the bomb chamber will be exothermic. If heat is evolved

i.e. the change in temperature is raised.

Endothermic Rxn:

If the heat is not evolved i.e. the temperature decreases then reaction will be

endothermic. The water should be stroked because if some heat is absorbed by the

stirrer or glass will be released.

Calorimetry:

The experimental procedure used to measure the heat evolved or absorbed during a

chemical reaction is called calorimetry.

Note:
1. Washing soap:

They are made from sodium and fats. So it is also called sodium soap.

2. Bath Soap:

They are made from potassium and fats. So it is also called bath soap.

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Exercise:

1. Choose the correct answer.

i. H per mole is expressed in units of:

(a) KJ (b) 0F (c) 0C (d) K

ii. Which one of the following is not a state function.

Heat
(a) Enthalpy (b) (c) Temperature (d) Pressure

iii. for solids and liquids

(a)
H = E (b) H > E (c) H < E (d) E = O

iv. 1 k-cal is equal to:

(a) 41.8 103J (b) 418 103J (c) 4.18 103J (d) 0.418 103J

v. Standard enthalphy (H0) for 1 mole of a substance which exists in its natural

state of 1 atm pressure is measured at:

298L
(a) OK (b) (c) 273K (d) O 0C

vi. H can be measured indirectly by applying:

(a) Avogadros law (b) Gas laws (c) Hesss law (d) Faradays law

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vii. Enthalpy mans:

(a) Disorder (b) Transition state (c) Rate constant (d) Heat content

viii. No work is done at constant:

(a) Pressure (b) Volume (c) Temperature (d) Mass

2. Appling Hesss law calculate H0 for the sublimation of one mole of

iodine from the following equation:

Given: i) H2(g) + I2(g) 2HI(g) H0 = 51.8 KJ/mol

ii) H2(g) + I2(g) 2HI(g) H0 = 10.5 KJ/mol

Solution:

I2 I2(g) Hsub = ?

Reversing the given equation (ii) we get equation

2HI(g) H2(g) + I2(g) H0 = + 10.5 KJ/mol

Now add this equation (iii) to equation (i)

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H 2( g ) I 2 ( g ) 2 HI (g) VH 0 51.8 KJ / mol

2 HI (g)
H 2( g ) I 2( g ) VH 10.5 KJ / mol

I 2( g ) I 2 ( g ) VH sub 62.3

i)

3. Calculate the heat of formation of an aqueous solution of NH4Cl from the

following data.

i) NH3 + aq NH3 H0 = 35.1 KJ/mol1

Hcl(j) + aq Hcl H0 = 72.41 KJ/mol1

NH3 + Hcl NH4cl H0 = 51.48 KJ/mol1

Solution:

H 3( g ) aq 2HI 3 ( aq ) VH 0 35.16 KJmol 1

Hcl ( g ) aq Hcl ( aq ) VH 0 72.42 KJmol 1

NH 3 Hcl( aq ) NH 4 cl( aq ) VH 0 72.41 KJmol 1


NH 3( aq ) Hcl ( aq ) NH 4 cl( aq ) VH 0f 159.05KJmol 1
i)

4. Liquid ethanol when burnt n oxygen at 250C H0 = -1402.14KJ mol1.

The heats of formation of H2O are 33.50 and 285.81 KJ mol1 respective

at the same temperature. Calculate the heat of formation of ethanol at

250C.

Required:
H0f of formation of ethanol, C2H5OH=?

Solution:

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2C + 3H2 + O2 C2H5OH Hf0 = ?

Data Given:

i) C2H5OH + 3O2 2CO2 + 3H2O H = 1402.14Kg

ii) C+O2 CO2 H = 33.5 Kg

iii) H2 + O2 H2O H = 857.42Kg

by reversing equation (i), we get equation (iv)

iv) 2CO2 + 3H2O C2H5OH H = + 1402.14

Multiplying equation (ii) by 2, we get equation (v);

v) 2C + 2O2 2CO2 H = 2 (393.5) = 787.5Kg

vi) 3H2 + 3/2 O2 3H2O

By adding (iv), (v) and (vi)

2 CO 2 3H 2O C2 H 5OH 3O2 VH 1402.14


iv)

2C 2O2 2 CO 2 VH 787.5
v)

2 H 2 3 O2 CH 5O VH 875.42
2
vi)
2C + 2H2 + O2 3H2O H = +1402.14-1644.3 = 242.79

9. Explain the following short questions with reasons. Total energy of the

system and its surrounding remains constant.

Ans. According to first law of thermodynamics. Total energy of the system and

surrounding remains constant.

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Let us consider a gaseous system with energy E1 at its initial state. Now q amount of

heat is supplied to the system from outside the system. The total energy will become

E + q. If the piston moves up, the work W will be done by the system. Energy is

consumed is doing this work. The energy at final state of the system will be E2.

E2 = (E2 + q) w

E2 E1 = qw

E2 = q w (i)

q= E + W (ii)

i. The heat supplied to the system, increased the internal energy of the system

and did work of expansion.

ii) It is essential to mention the physical state of the reactants and the product in

thermochemical equation.

Ans. Melting of a solid (heat of fusion)

During melting of ice the temperature remain constant at O0C until all the ice has

melted. During changes of state from ice to water, heat is obsorbed to over come the

force of attraction. The heat content of water is higher than the ice, all thought both

has the same temperature of O0C. In thermochemistry the heat content of a substance

is very important.

For example

H2O(g) H2O Hf = 334KJ/mol

b. Boiling of liquid (heat of vaporization)

The heat obsorbed to convert one mole of liquid into vapours at its boiling point is

called heat of vaporization.

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Explanation

During the process of change of physical state from liquid in to vapour requires

energy that cannt observed by rise of temperature. It means that heat content of

vapours is higher than for liquid. E.g.

H2O1 H2O(g) Hf = 40.65 KJ/mole

(Ionic reaction are very fast)

Ans. The ionic reaction are fast because the appositely charged ions are attract each

other. When an ionic compound is dissolved in water.it dissociated into ions which are

free to move. Due to effective collision the reactions among the appositely charged

ions is very fast. The work done has positive and negative values.

Ans. According to the sing convention (i) work done by the system on the

surrounding will e-w (b) work done on the system by the sourrounding will be tw. (v)

the exothermic reaction are spontaneous.

Ans. A process that occurs by its own without any help are called spontaneous

changes. These change have a natural tendency to occur with out supply of external

energy. These change are unidirectional flow of water form higher level to lower

level, colling of tea. Buring of natural gas and rusting of iron.

Burning of carbon: C + O lor + heat burning of natural gas CH, + 2O 2 CO2

+ 2HO + Heat.

Standard heat of combustion is always

Ans. According to sign convection the heat evolved during a reaction will be

denoted by H = KJ/Mole. When combustion occurs at standard conditions of O 0C

and one atmosphere pressure, is called standard of combustion.

Enthalpy change is state function

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A quantity is called a state function when its value depends only on that state and not

on the path or route used to go from one state to another. Since enthalpy is state

function. This statement is known as Hesss law. For exemption the heat of formation

of corbon dioxide will be 393.5 KJ/mole weather the reaction occur in one step or in

servel step.

Heat is not a state function.


Mechanical work and heat are quantitative process because their values depends on

the specific transition or path between two equilibrium state. The heat content of a

system can be calculated by q = MCT.

Where M is the mass, C is the specific heat capacity and T is the change in

temperature.

Ans. Change in enthalpy H occurs at constant pressure, in cause of solid or liquid

occurs. It means no work is done. The heat observed increased only the uitemal

energy of the system. E endothermic reactions are always written with a positive

sing.

Ans. According to the sign convention the heat observed during reaction will be

enoted by H = + KJ/mol. For example: Freezing of water pumping of water from

owner to higher level, compressing a gas by Appling pressure, boiling of water and

decomposition of water by electrolysis.

H2O (i) H2O(g) Hf = 4065J/M

HZQ(s) H2O(1) Hf = 334KJ/Mol.

1. State and explain Hesss Law of constant heat summation. Show that it is

a direct consequence of the first law of thermodynamics.

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Ans. Hesss Law: the heat evolved or absorbed will be the same if the reaction

completes ibn one step or several steps.

It means it is another form of the first law of thermodynamics which is based on the

law of conservation of energy.

b) Determine H0 for the following reaction.

2C + 2H2 C2 H4(g) H0 = ?

i) C(s) + O2(g) CO2(g) Hoi = -393.29 KJ mol1

ii) H2 + O2(g) H2O(g) H02 = 285.7 KJ mol1

iii) C2H4(g) + 3O2(g) 2CO2(g) + 2H2O(g) H03 = 1430.2 mol1

Solution:
2C(s) + 2O2(g) 2CO2(g) H01 756.58 KJ mol1

2H2 + O2 2H2O H02 = 571.4 KJ mol1

Reversing equation (iii)

iii) 2 CO2 + 2H2O C2H4(g) + 3O2 H03 = + 1430.2

Now adding equation (i), (ii), & (iii)

2C(s) + 2H2(g) C2H4(g) H03 = + 72.14 KJ mol1

6. a) What do you mean by state of a system? What are state function?

Ans. See text Q. No. 7

b) A chemical reaction takes place in a container of crossectional area 100cm2

filled with a weightless and frictionless piston. The piston is moved up

through 10 cm against an external pressure of 1 atmosphere as a result of the

reaction. Calculate the work done by the system.

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Sol: Area A = 100cm2

Distance covered by the piston L = 10cm pressure p = 1 atm

Change in volume V = A L = 100 10 = 1000 cm3

Work done W = PV = 1 1000 atm. Cm3

10. Enthalpy of neutralization of strange acid and strong bases has always the

same value.

Ans. Heat or enthalpy of neutralization:

This is amount of heat evolved when one mole of H + ions from an acid reacts with

one mole of OH ions from an alkali.

Thus the heat of neutralization of NaH by Hcl is 57.36 KJ. This amount of heat is

evolved when 40g (1 mole) of NaOH reacts with 36.5g (1 mole) of Hcl.

NaOH + Hcl Nacl + H2O

H+ + OH H2O H = 57.35 KJ/mol

11. H0 and E have the same value for the reaction taking place in solution.

Ans. Change in enthalpy H occurs at constant pressure. In case of solution change

in pressure is not important because no change in volume of solution occurs. It means

no work (PV) is done. The heat absorbed increases only the internal energy of the

system, E.

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