Lecture 9

First Law (Contd.)

9.1 Thermochemistry (Contd.)

We have seen in the previous lecture that reaction enthalpy at standard conditions can
be computed as:
◦
∆r H 0 = ∑ νi H i
i
However, in the experiments, we measure ∆H and not H directly. Absolute enthalpies
are not known. For this purpose, we define reference states for each substance. The
reference state is taken as the stoichiometric amounts of the elements in the substance,
each in its standard state, at a given temperature. We define relative enthalpies called
enthalpy of formation (∆ f H ◦ ). This is defined as the enthalpy for the reaction in which
one mole of the substance in its standard state at the given temperature is formed from
its elements, each in its standard state. Since same reference states are used for reactants
and products, we can write:
∆r H ◦ = ∑ νi ∆ f Hi◦
i

Enthalpy of formation is an intensive quantity and has the unit J mol−1 .

At 25◦ C, the reference form is usually the most stable form of the element at 25◦ Cand
1 bar pressure. Thus the reference form of hydrogen is H2 (g) instead of H(g). The
reference form of carbon is graphite, and the reference form of sulfur is rhombic sulfur.
In any case, the enthalpy of the formation of an element in its standard state is zero
at every temperature. Enthalpy of formation at 25◦ C is available in thermodynamic

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tables. Using this data, we will be able to calculate ∆r H ◦ .
Consider the example,

1
C(graphite) + O2 (g) → CO(g)
2

at 298 K and 1 bar pressure. It is not practical to measure ∆r H for the reaction, as some
are converted directly to CO2 . The following strategy can be used:

• In excess O 2

C(graphite)+O2(g)→CO2(g) ΔrH0=-393.509 kJ mol-1

CO (g) + ½O2(g)→CO2(g) ΔrH0=-282.984 kJ mol-1

Writing the above as:

C(graphite)+O2(g)→CO2(g) ΔrH0=-393.509 kJ mol-1
CO2(g)→ CO (g) + ½O2(g) ΔrH0= 282.984 kJ mol-1

C(graphite)+ ½O2(g) →CO(g) ΔrH0=-110.525 kJ mol-1

See the below figure for how the reference (zero) enthalpy is affecting the overall
calculation:

Enthalpy Level Diagram

C(g)+2O(g)

716.68

1215.02
C(s)+2O(g)
in kJ mol-1

498.34

C(s)+ O2(g)
Zero
-110.53
CO(g)+ ½O2(g)
fH
-393.51
-282.98
CO2(g)

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 Take the example:
CO2 (g) + C(graphite) ⇌ 2CO(g)

From the tables, we have ∆ f H ◦ of CO2 ( g) are CO( g) are -393.509 and -110.525, respec-
tively. Then,
∆r H ◦ = 2∆ f H ◦ (CO(g)) − 1∆ f H ◦ (CO2 (g)) − 1 × 0

Note that it is practically difficult to experiment where CO2 (g) reacts with graphite to
give CO(g) and measure ∆r H. Thus, the above strategy is a very useful approach to
predict ∆r H for such reactions without attempting to do it directly in the laboratory.
For calculating reaction enthalpy at any other temperature, using the values from
the thermodynamic table at 298 K, one may use the heat capacity data on the reactants
and the products (see the image and the derivations below).

Δr HT∘
reactants products
298K T

∫T ∫298K
CP,reactant dT CP,product dT
Δr H298
∘
K
reactants products

Figure 9.1: Thermodynamic cycle to compute ∆r H ◦ at any temperature T from ∆r H ◦ at 298 K

and CP data.

Z 298 Z T
∆r HT◦ = CP,reactant dT ◦
+ ∆r H298 + CP,product dT
T 298
Z T
◦
∆r H298


= + CP,product − CP,reactant dT
298
Z T
◦
= ∆r H298 + ∆r CP◦ dT (9.1)
298

Here,
◦
∆r CP◦ = ∑ νi C P,i
i
Note that, the above relationships between CP and ∆r H can be derived in a straight-

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forward manner:

∆r H = ∑ H (products) − ∑ H (reactants)
∂ ∑ H (products) ∂ ∑ H (reactants)
     
∂∆r H
= −
∂T P ∂T P ∂T P

= ∑ CP,products − ∑ CP,reactants (9.2)

9.2 Calorimetry

Heats of reactions can be measured by adiabatic calorimeters. The reaction occurs in a

container that is immersed in water. The whole setup is insulated, and no heat exchange
occurs. An opening in the calorimeter makes sure that it is kept at a constant pressure.
The following reactions can be considered to take place in the calorimeter:
Here “cal” means a container, thermometer, stirrer, and the measured amount of water

ΔHT2
R(T2) + cal (T2) P(T2) + cal (T2)

ΔHR ΔHA = 0 ΔHP

R(T1) + cal (T1) P(T1) + cal (T1)

ΔHT1

within the calorimeter. Since the process of R converting to P is an adiabatic process,

∆HA = 0 (adiabatic enthalpy change). As enthalpy is a state function, we can write

∆HA = ∆H ( T1 ) + ∆HP = 0

∆HA = ∆HR + ∆H ( T2 ) = 0

Considering heat capacities of the reactants, products, and calorimeter are constant over
the range of T1 to T2 , we have

∆H ( T1 ) = −∆HP = − [CP (P) + CP (cal)] ( T2 − T1 )

∆H ( T2 ) = −∆HR = − [CP (R) + CP (cal)] ( T2 − T1 )

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Thus, we can obtain ∆H for the conversion of R to P (given amount) at either T1 or T2 .
∆r H can then be determined as
∆H/∆ξ

If CP is unknown, then that can also be computed using the adiabatic calorimeter.
It can be done by heating the sample at constant P with an electric coil. The heat
46 2 THE FIRST LAW
generated by an electric coil = I 2 Rt, where R, I, and t are the resistance, current, and
time, respectively. Then, by measuring ∆T, we can estimate CP = I 2 Rt/∆T.
back to the surroundings. A
One can also do similar experiments in a bomb calorimeter, where when the heating
the volume of the occurs at
implies a larger heat capacity
reaction chamber is kept constant (e.g., steel bomb).
constant pressure of a syste
We show later (Section 2.11
capacities of a perfect gas:
Cp − CV = nR
It follows that the molar hea
constant pressure than at con
ume of a monatomic gas is a
and must be taken into accou

IMPACT ON BIOCHEMISTRY
I2.1 Differential scanning c
Fig. 2.15
A differential Scanning A differential
Calorimeter (DSC) scanning calorimeter.
is a more A differential
accurate instrument scanning calorim
to measure
The sample and a reference material are frompan
a sample at constant p
∆H and CP . DSC has a reference pan and a sample pan. The reference is empty,
heated in separate but identical metal heat
‘differential’ refers to the fac
sinks.the
and the sample pan holds Thesample
output under
is the difference
study. Thein power
temperature of the two pans
needed to maintain the heat
a reference material which do
sinks at equalThe temperature of both
is monitored by accurate thermocouple-based thermometers. analysis. The term ‘scanning’
temperatures as the temperature rises.
pans is kept the same throughout the experiment. The amount of heatreference material
required to keep are increa
A DSC
the temperature of both pans the same is monitored as a function of time. The consists
change of two sma
rate. The temperature, T, at
initial temperature and α is t
ΔH melting ΔH
Heat ow computer controls the electr
J/s CP
Exothermic ature in the sample and refere
Endothermic
Tmelting The temperature of the sam
T T
material if a chemical or ph
occurs in the sample during
in heat/per time (in J/s) is plotted against the temperature. CP of material and ∆H ofexcess energ
compartments,
a phase transition can be measured as shown in the figure above. process. For example, an end
relative to that of the refere
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strongly than the reference in
If no physical or chemical
the heat transferred to the s
 Interesting reading:
https://openstax.org/books/chemistry-2e/pages/5-2-calorimetry