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2 Enthalpy and Enthalpy Change

CONCEPT OF ENTHALPY
▪ Enthalpy (H) is an extensive property of a substance that can be used to obtain the
heat absorbed or released in a chemical reaction.
▪ The heat content of the system is known as the enthalpy of the system.
▪ The total heat absorbed or liberated in a chemical reaction is called the heat of
reaction.
▪ We cannot measure the absolute value of the enthalpy of the system, but we can
measure the change in enthalpy.
▪ The experimental technique for measuring enthalpy changes is called calorimetry.
▪ Calorimeter is a device for measuring quantities of heat.
 Calorimeter – a device for measuring heat change of a process

Constant volume calorimeter → bomb Constant pressure calorimeter →

calorimeter coffee cup calorimeter
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 CONCEPT OF ENTHALPY
• The symbol for the change in enthalpy is ∆H.
• Enthalpy (H) is measured in the units of kJ.
• The change in enthalpy for a reaction at a given temperature and pressure is
obtained by subtracting the enthalpy of the reactants from the enthalpy of
products (∆H). Or it is difference between the enthalpies of the products and
the enthalpies of the reactants.
 Enthalpy Change
For a reaction A + B C + D,

∆H = Total enthalpy of the products – Total enthalpy of the reactants

= H2 – H1

Where H2 = (HC + HD) and H1 = ( HA + HB)

∆ H = H final - H initial
∆ H = H product - H reactant

For endothermic reactions H final>H initial and H is positive(+H)

For exothermic reactions H final<H initial and H is negative(-H)
 Enthalpy (H)

internal energy plus the product of pressure and volume

U = internal energy
H = U + PV P = pressure H, U, P and V are state properties
V = volume

Since ∆U = q + w
If process carried under constant pressure and only expansion of volume allowed
w = - P∆V
∆U = - P∆V + q ….. (1)
q = ∆U + P∆V
q is heat released at constant pressure
Since H = U + PV
∆H = ∆U + ∆PV at constant pressure
▪ Energy transferred as heat at constant
pressure is equal to the change in enthalpy
Since ∆U = - P∆V + q (1)
of a system (qp = ΔH)
∆H = ∆U + P∆V ▪ Enthalpy changes are measured in a
 = - P∆V + q + P∆V constant-pressure calorimeter
=q
∆H = qp

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 TYPES OF ENTHALPY
TYPES OF ENTHALPY
A. Enthalpy of Reaction, ∆H◦rxn
B. Enthalpy of Formation, ∆H◦f
C. Enthalpy of Combustion, ∆H◦c
D. Enthalpy of Neutralization, ∆H◦neut
E. Enthalpy of Hydration, ∆H◦hydr
F. Enthalpy of Solution, ∆H◦soln

Standard states conditions for measuring the enthalpies are

1. Temperature of 25˚C (298K)
2. Pressure of 1 atm (101kPa)
3. Solution having concentration of 1M
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 TYPES OF ENTHALPY
Standard Enthalpy of Formation ∆H◦f
is the heat change that results when one mole of a compound is formed from its
elements at a pressure of 1 atm.
The standard enthalpy of formation of any element in its most stable form is zero.
∆Hºf(O2) = 0 ∆Hºf(C, graphite ) = 0

∆Hºf(O3) = 142 kJ/mol ∆Hºf(C, diamond) = 1.90 kJ/mol

For example
C (graphite) + O2 (g) CO2 (g)

∆Hºf(CO2) = -393.5 kJ/mol

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 TYPES OF ENTHALPY
Standard Enthalpy of Reaction ∆H◦rxn
is the enthalpy change of a reaction measured at standard conditions.
2SO2 (g) + O2 (g) 2SO3 (g) ∆H◦rxn = -192.0 kJ/mol
SO2 (g) + ½O2 (g) SO3 (g) ∆H◦rxn= -96.0 kJ/mol

Standard Enthalpy of Combustion ∆H◦c

is the enthalpy change when one mole of pure substance is completely burned in
excess oxygen under the given temperature and pressure of the reaction.
CH4(g) + 2O2(g) 2CO2(g) + 2H2O(l) ∆H◦c = -890.0 kJ/mol

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 Heat of reaction
 Heat of reaction : the total heat absorbed or released in a chemical reaction.
 Constant volume conditions are often inconvenient and sometimes impossible to
achieve. Most reactions occur under constant pressure usually at atmospheric
pressure.
 If the reaction is performed at constant pressure (eg: in a coffee cup calorimeter) ,
therefore the heat of reaction (qp) is equal to enthalpy change (∆H)

Standard states – usually shown as degree sign (°)

 For a gas , the standard states are pressure = 1 atm and the gas behave ideally
 For a substance in aqueous solution, the molar concentration = 1M
 For pure substances (elements or compounds), the standard state is in their most
stable form at pressure = 1 atm and temperature = 25°C

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 Calculation of Heats of Reaction using ∆Hº f
• ∆H˚reaction = sum of ∆Hºf of the products – sum of ∆Hºf of the reactants

aA + bB → cC + dD

• ∆H˚reaction = ∑ ∆Hºf (products) - ∑ ∆Hºf (reactants)

= { c(∆Hºf [C]) + d(∆Hºf [D]} - { a(∆Hºf [A]) + b(∆Hºf [B]}

• The standard enthalpy of formation for carbon dioxide, ethane and water are -393, -85 and -286
kJ mol-1 respectively. Calculate the heat for the following reaction
• C2H6 (g) + 7/2 O2 (g) → 2CO2 (g) + 3H2O (ℓ)

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Info

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