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Thermochemistry

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7 views49 pages

Thermochemistry

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amnaagh12
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© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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The process in which thermal energy is converted into mechanical

energy and vice-versa is called Thermodynamics.


Thermochemical Reactions
The reactions in which material change is accompanied by heat energy change is
called a thermochemical reaction.
There are two types of thermochemical reactions:
i) Endothermic Reactions:
Heat is absorbed in endothermic reactions. The enthalpy value (ΔH) is
positive for endothermic reactions.
For example: CaCO3  CaO + CO2 ΔH=+ve
ii) Exothermic Reaction
Heat is released in exothermic reactions. The enthalpy value (ΔH) is
negative for endothermic reactions.
All the combustion reactions are exothermic in nature.
For example: C + O2  CO2 ΔH=-ve KJ/mol
Thermodynamic Terms
System: Any real or imaginary portion of the universe which is under
examination is called a system. System may be homogenous (single
state) or heterogeneous (more than one state).
Types of System: There are 3 types of system.
1. Open System: Both energy and mass can be transferred.
2. Closed System: Only energy can be transferred.
3. Isolated System: Neither energy nor mass can be transferred.
Surrounding: The part of Universe around the system.
Boundary: The border between system and surrounding.
State: P, V, T, E & H are called state of a system.
Macroscopic Properties
The properties of a system in bulk which are easily measurable are
known as the macroscopic properties.
e.g: Pressure, Temperature, Volume etc.
Intensive Properties: Independent of amount.
example: Density, Pressure, Temperature, viscosity, surface tension,
refractive index, melting point, boiling point etc.
Extensive Properties: dependent of amount.
Example: Mass, Volume, Mole, Enthalpy, Entropy (disorderness of
system), Internal energy etc.
First Law of Thermodynamics
(Law of conservation of Energy)
Helmholtz - 1847
Statement:
“Energy can neither be created nor destroyed but it can be
changed from one form to another.”
“Total energy of system and surrounding always remain
constant.”
If ‘q’ be the heat provided to a system from surrounding
then it changes the internal energy ‘ΔE’ of the system and
the system does work ‘W’ by lifting the piston up.
q= ΔE+W
q is positive if heat is absorbed, negative if heat is released
W is positive if work is done by the system, negative if work is done on
the system
Q#6 (b) Page#163
In a certain process 848 J of heat is absorbed by a system, while 394 J
of work is done on the system. What is the change in the internal
energy for the process?
Q#7 (a) Page#163
If 1800 cals, pf heat is added to a system while system does work
equivalent to 2800 cals by expanding against the surrounding. What is
the value of ΔE for the system?
Q#7 (b) Page#163
In a certain process, 500 J of work is done on a system which gives off
200 J of heat. What is the value of ΔE for the process?
Derivation
Pressure – Volume Work Equation
Consideration:
Consider a cylinder of a gas having
an area of cross section ‘A’ fitted
with a frictionless and weightless
piston.
Case (a) Process at constant volume
Case (b) Process at constant pressure
Enthalpy:
The total heat content of a system is called enthalpy. It is denoted by H.
H=E+PV
Change in Enthalpy (ΔH):
The amount of energy absorbed or released at constant pressure is
called change in enthalpy (Δ H)
Numerical
When 4000 J heat is added to a gaseous system at a constant pressure
of 101300 N/m2, its internal energy increases by 500 J. Calculate the
change in volume of the system. (2015)
Thermochemistry
The branch of chemistry which deals with thermochemical reactions.
1 Cal=4.184 J
Hess’ Law of Constant Heat of Summation
Statement:
“The total enthalpy change remains constant
either in direct method or indirect method.”
Explanation:
Consider a chemical reaction in which reactant
‘A’ changes to the product ‘D’ in a single step
with ΔH as the enthalpy change. It may proceed
through different intermediate stages i.e, ‘A’ first
changes to ‘B’ with enthalpy change ΔH1, ‘B’ then
change to ‘C’ with enthalpy change ΔH2 and
finally ‘C’ changes to ‘D’ with heat change as
ΔH3.
According to Hess’ law:
ΔH= ΔH1 + ΔH2 + ΔH3
Application of Hess’ law
CO2 gas reacts with excess of NaOH to give Na2CO3 with enthalpy
change -90 KJ/mole. This reaction may be carried out in two steps. I the
first step the enthalpy change is -49 KJ/mol and in the secon step the
enthalpy change is -41 KJ/mol. Hence according to Hess’s law:
ΔH= ΔH1+ ΔH2
ΔH=-49-41=-90 KJ/mol
Heat of Formation
The change in enthalpy when 1 gram mole of a substance is formed
from its elements.
It is denoted by ΔHf

Since graphite is the most stable allotrope of carbon so it has been


assigned a heat formation value that is nearly equal to 0.
The heat of formation of elements is equal to 0.

Standard Heat of formation (ΔH°f) at 25 °C and 1 atm.


The Born-Haber Cycle
• It is the best application of Hess’s law
• It states that energy change in a cyclic process is always zero.
ΣΔH(cycle)=0
• It enables us to calculate the lattice energy of ionic compounds.
Enthalpy of Neutralization (ΔH°n)
The amount of heat evolved when 1 mole of water is formed I
neutralization reaction is called enthalpy of neutralization.

Enthalpy of neutralization of strong acid with a strong base always


remain same i.e -57.4 KJ/mol.
Enthalpy of Combustion
It is always negative.

It is calculated by a BOMB CALORIMETER in which volume remains


constant.
Spontaneous Reaction
• Does not require any external aid for completion. For the start they may
need energy.
• The reactant releases energy in these reactions
• They occur in nature.
• They cannot be reversed.
Example: Evaporation.
Example: water flowing down the hill.
Example: Neutralization
Example: CuSO4 + Zn  ZnSO4 + Cu
Example: burning of coal
Non Spontaneous Reaction
• Water pumping up the hill.
• Refrigeration
• Haber-Bosch Process

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