Lecture 8

First Law (Contd.)

8.1 Thermochemistry

The quantity of heat evolved or absorbed in a chemical reaction or phase change can
be determined by measuring temperature change in an adiabatic process. Enthalpy is
an extensive quantity. Then, for a given T and P,
Ns
dH = ∑ H i dni
i

Here Ns is the number of species and H i is the molar enthalpy of species i.

dH = dq P = ∑ H i dni
i

Chemical reactions can be written as

Ns
0= ∑ νi Bi
i

where νi is called stoichiometric numbers and Bi is the molecular formula. νi s are

dimensionless. They are positive for products and negative for reactants. Let ξ be the
extent of reaction, and has the units of number of moles.

ni = ni,0 + ξνi

where ni,0 is the amount of component i at initial time, and ni is the amount at current
time.
dni = νi dξ

1
 N
dH = d̄ q P = ∑ νi H i dξ
i

 
∂H d̄ q P
∆r H =
∂ξ
=
dξ
= ∑ νi H i (8.1)
T,P

Here, ∆r H is the reaction enthalpy.

If one mole of a reaction occurs, then ∆ξ = 1 mol and ∆H = (1mol × ∆r H ).
Since balanced equation can be always written by dividing or multiplying by an
integer throughout, the number of moles of a reaction varies in the way it is written.
Enthalpy of reaction for
2H2 + O2 ⇋ 2H2 O

is twice that of the reaction

1
H2 + O2 ⇋ 2H2 O
2
Note that, the units of ∆r H is J mol−1 and mol−1 refers to a mole of reaction for the
reaction as it is written.
For standardization, we consider reactants in their standard states are getting con-
verted to products in standard states.

◦
∆r H 0 = ∑ νi H i
i

Standard states are defined at a given temperature as:

• Pure gaseous susbstance (denoted by g): ideal gas at 1 bar.

• Pure liquid (denoted by l): pure liquid at 1 bar pressure.

• Pure crystalline solid (denoted by s): pure crystalline solid at 1 bar

• Solutions: we will discuss this later.