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3 ‫محاضرة‬ ‫ احمد جياد‬.‫م‬.‫م‬

Enthalpy
Enthalpy is a thermodynamic property

Main unit: J

For practical reasons, most chemical reactions are typically not carried out at constant
volume. They are usually carried out in systems open to the atmosphere and so they are at
constant pressure, typically one atmosphere. The change in energy of a system at constant
pressure, when the only work done by the system is pressure-volume work, is given by:

ΔEp = qp + wp first law or thermodynamic

W =P ∆V → ΔEp =qp –PΔV

E2 – E1 = qp– p(V2 – V1)

The heat energy (the amount of heat absorbed) is given by:

q= (𝐸2 + 𝑃𝑉2 ) − (𝐸1 + 𝑃𝑉1 )

Since the heat quantity is given by the difference between two quantities of the two function
state of the system, so it is suitable to insert a new function, which is the enthalpy(H),
where:

𝐻 = 𝐸 + 𝑃V

Enthalpy is the total thermal energy of the system. It is equal to the internal energy of the
system plus the product of pressure and volume. In a physical sense, it can be viewed as the
energy required to create the system at equilibrium (internal energy) plus the amount of
energy required to create space for the system by expanding its volume against a constant
pressure (PV). This new state function allows us to be able to predict the changes in energy
for chemical reactions at constant pressure. Although the value of enthalpy for an
equilibrium state cannot be calculated directly, the change in enthalpy (ΔH) between
equilibrium states can be calculated and is given by:

∆𝐻 = ∆𝐸 + ∆(𝑃𝑉 ) = q + W + Δ(𝑃𝑉 )

For chemical reactions at constant pressure, where the only work done by the system is
pressure-volume work, WP is equal to PΔV and the change in enthalpy becomes ;

ΔHp = qp - PΔV + PΔV

ΔHp = qp So the equation becomes: qp = 𝐻2 − 𝐻1 = ∆HP

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Heat Capacity
Heat capacity (symbol C) is defined as the ratio between the amount of heat energy
transferred to the object and the resulting increase in temperature of the object. heat capacity
is expressed in units of joules per kelvin(J.K-1).

And and the specific heat capacity, often simply called specific heat, which is the heat
capacity per unit mass of a material.( J • g-1 • K-1 or cal • g-1 • K-1)

NOTE: - Heat capacity = specific heat × mass

Molar heat capacity, which is the heat capacity per mole of a pure substance. (J • mol-1 • K-1
or cal • mol-1• K-1).

Heat capacities are extensive properties: 100 g of water, for instance, has 100 times the heat
capacity of 1 g of water (and therefore requires 100 times the energy as heat to bring about
the same rise in temperature).
𝑞
C= (1)
∆𝑇
C= heat capacity , q= heat , T= Temperature

Specific heat of gases: - When a gas is heated, it expands and the volume increases if we do
not allow the gas to expand then the pressure will increase. By allowing the gas to expand
the pressure is maintained a constant and gas does some amount of mechanical work against
the atmospheric pressure at the cost of its heat energy

. In the case of gases a change in temperature causes a considerable change in the pressure
and volume .and hence there are two specific heats

1) Specific heat at constant pressure (Cp): It is defined as the quantity of heat required to
raise the temperature of 1mole of a gas through one kelvin at constant pressure.

2) Specific Heat at constant Volume ( CV): It is defined as the quantity of heat required to
raise the temperature of 1mole of a gas through one Kelvin at constant volume.

From eq. (1):

𝑑𝑞 = 𝐶 𝑑T

𝑑𝑞 = 𝐶𝑉 𝑑T system at constant volume

𝑑𝑞 = 𝐶p 𝑑T system at constant pressure

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The Cp value differs from the C v value because when the system volume changes, it does a
work, and That means that a part of the heat supplied for the system turns into a work used to
expand the system, where after making some derivations of the difference between Cp and Cv
Identified by the following equation:
𝜕𝐻 𝜕𝐸
𝐶𝑃 − 𝐶𝑉 =( )𝑃 − ( )𝑉
𝜕𝑇 𝜕𝑇

𝜕𝐻 𝜕𝐸
R = ( )𝑃 − ( )𝑉
𝜕𝑇 𝜕𝑇

𝐶𝑃 − 𝐶𝑉 = R Mayer’s Relation

Where R represents the additional energy required to heat a mole of ideal gas at constant
pressure which is more than the energy required for heating at constant volume.

Dependence of internal energy on temperature and volume:

Internal energy is a function of two variables that determine the system, temperature and
volume:

E=f(T,V)

The derivative of internal energy as a result of a change in temperature and volume is given
by the following relationship:
𝜕𝐸 𝜕𝐸
dE = ( )𝑉 𝑑𝑇 + ( ) 𝑇 𝑑𝑉
𝜕𝑇 𝜕𝑉

Where the first term of the relationship represents the change in the internal energy that
results from temperature change only, while the second term represents the change in the
internal energy resulting from volume change alone

And if we take into consideration that the volume is constant, then:

𝜕𝐸
dE = ( )𝑉 𝑑𝑇 = CVdT
𝜕𝑇

𝑇
dE = ∫𝑇 2 𝐶𝑉 𝐶𝑑 𝑇
1

∆E=CV∆T

Where this equation is applied when assuming that the C V is not temperature- dependent.
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Dependence of enthalpy on temperature and pressure:

Enthalpy is a function of two variables that determine the system, temperature and pressure:

𝐻 = 𝑓(𝑇, 𝑃)

And if we take the partial derivative of enthalpy result:

𝜕𝐻 𝜕𝐻
dH = ( )𝑃 𝑑𝑇 + ( ) 𝑑𝑃
𝜕𝑇 𝜕𝑃 𝑇

and at constant pressure then:-

𝜕𝐻
dH = ( ) 𝑑𝑇 = 𝐶𝑃 𝑑𝑇
𝜕𝑇 𝑃

∆ H= 𝐶𝑃 ∆𝑇

Example: Calculate ∆E when heating 55.4 g of xenon gas from a 300 absolute to 400
absolute where CV= 12.47 𝐽.𝐾 −1 . 𝑚𝑜𝑙−1. assume that the heat capacity at constant volume
does not depend on temperature?

Solution:
𝑇
E = 𝑛𝐶𝑉 ∫𝑇 2 𝑑𝑇 = 𝑛𝐶𝑉 ∆𝑇∆
1

55.4
= × 12.47 × (400 − 300)
131.3

= 0.4219 × 12.47 × 100 = 526 J

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