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THERMOCHEMISTRY
Definition:
The branch of chemistry which deals with the heat evolved or absorbed during a
Or
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.
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
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2. Decomposition of KNO3
Note:
Chemical change is nothing but the breaking of old bonds and formation of new
bonds.
1. Thermochemical Equation:
That equation which shows;
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;
c. Strength of bonds.
If H= + ve:
It means that;
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.
If H= - ve:
It means that;
2. Reaction is exothermic.
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
It goes from non equilibrium state to It goes from equilibrium state to non
v. Irreversible. v. Reversible.
It goes from unstable state to stable state. It goes from stable state to unstable state.
potential.
G = +ve
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should be negative. The H of non-spontaneous reaction is
positive.
H + (-) negative.
H = (+) positive.
x. Entrophy. x. Entrophy.
S = + ve S = - ve
The energy of the product is low. The energy of the product in non-
endothermic.
Note: soutanes process are mostly
process.
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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)
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
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
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
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
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.
4. If we know the values of some state function, the values of other can be found
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.
State Function:
These properties which describe the state of a system is called state variable or state
function.
It depends upon.
i. Initial State.
Initial State:
The condition of a system before a change occur is called initial state.
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.
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.
i. Translational Motion.
Potential Energy:
It is produced due to the position of particles and the position of particles is
i. Intermolecular Forces.
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Note:
It is impossible to determine the internal energy of a system but however change in
Mathematically:
E = E2 E1
Numerical Type
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
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Results of Internal Energy:
1. If internal energy increases the temperature and kinetic energy will be
increases.
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;
E2=E1+q (i)
iii. Due to heat the piston is pushed upward against the atmospheric pressure and
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E2=E1+q-W (ii)
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
And the heat given to a system is converted into internal energy only and since the
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Since;
E = q W
W=0
E = q 0
E = q
Since;
So,
E = q W
E = + W q=0
E = q +W
E = q W
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Sign Convention for Work And Heat:
If;
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
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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
E = ?
q=?
W=?
E q W
E qPV
Q W PV
E q PV
q=?
E = ?
W=?
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i. Isochoric 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
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
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
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
H = E + PV
Since;
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
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.
For example:
Most stable physical state of water is liquid state.
Representation:
H298
0
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MCQs:
The enthalphy of the element present in their elemental state is arbitrary zero.
Heat Capacity:
The amount of heat absorbed by a system to raise its temperature by one degree is
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
T 10 c
1 gram 1 gm
Heat
i.e.
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Unit:
J/ gm.k
Unit:
Its unit is KJ/mol
by one degree at constant pressure is called molar heat capacity at constant pressure.
It is represented by Cp.
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
Or
The enthalphy changes of a system depends upon its initial and final state and is
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
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.
Reaction:
C O2 CO2
(s) (g)
excess
H 393kJ / mol
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
i. Direct Method:
In this method CO2 is reacted with sufficient sodium hydroxide to from Na 2CO3 the
Reaction:
2 NaOH CO2 Na2CO3 H 2O
H 89 kJ / mol
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
It is the experimental verification of Hess Law for the calculation of Latie energy of
Statement:
That Cycle which is used for the experimental determination of Latice Energy of an
Principle:
It is based on the principle that net energy change during cyclic process will be
zero.
Note:
Explanation:
Latice energy is the amount of energy when one mole of 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
Step I (Sublimation):
Na Na
(s) (g)
H 108.84 kJ / mol
(s)
In this step the gaseous sodium is converted into gaseous ions. The energy required is
Na Na 1e
(g)
H 443.7 I .P
(s)
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Step III (Heat of Disassociation):
H 242
Cl ie Cl
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.
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
Reason:
Because;
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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
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
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
The amount of heat evolved or absorbed in 2 chemical reaction in which the reactants
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
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
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.
H = m x s x T
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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
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
Calorimetry:
The experimental procedure used to measure the heat evolved or absorbed during a
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:
Heat
(a) Enthalpy (b) (c) Temperature (d) Pressure
(a)
H = E (b) H > E (c) H < E (d) E = O
(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
298L
(a) OK (b) (c) 273K (d) O 0C
(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
Solution:
I2 I2(g) Hsub = ?
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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)
following data.
Solution:
The heats of formation of H2O are 33.50 and 285.81 KJ mol1 respective
250C.
Required:
H0f of formation of ethanol, C2H5OH=?
Solution:
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2C + 3H2 + O2 C2H5OH Hf0 = ?
Data Given:
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
Ans. According to first law of thermodynamics. Total energy of the system and
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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
ii) It is essential to mention the physical state of the reactants and the product in
thermochemical equation.
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
The heat obsorbed to convert one mole of liquid into vapours at its boiling point is
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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
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)
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
+ 2HO + Heat.
Ans. According to sign convection the heat evolved during a reaction will be
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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.
the specific transition or path between two equilibrium state. The heat content of a
Where M is the mass, C is the specific heat capacity and T is the change in
temperature.
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
owner to higher level, compressing a gas by Appling pressure, boiling of water and
1. State and explain Hesss Law of constant heat summation. Show that it is
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Ans. Hesss Law: the heat evolved or absorbed will be the same if the reaction
It means it is another form of the first law of thermodynamics which is based on the
2C + 2H2 C2 H4(g) H0 = ?
Solution:
2C(s) + 2O2(g) 2CO2(g) H01 756.58 KJ mol1
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Sol: Area A = 100cm2
10. Enthalpy of neutralization of strange acid and strong bases has always the
same value.
This is amount of heat evolved when one mole of H + ions from an acid reacts with
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.
11. H0 and E have the same value for the reaction taking place in solution.
no work (PV) is done. The heat absorbed increases only the internal energy of the
system, E.
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