Thermochemistry

Thermochemistry –branch of thermodynamics that deals with the heat involved in chemical and physical changes
Energy - capacity to do work or to transfer heat
Heat - energy transferred from hotter to colder object; heat is associated with the motion of particles in a substance.
Two forms of energy:
1) Kinetic Energy - the energy of motion: KE = 1/2 mv2
2) Potential energy - the stored energy that an object possesses due to its position relative to other objects or its
composition.

Example. An electron moving around the nucleus has KE due to motion and PE due to its attraction to protons in
the nucleus.

1 𝑐𝑎𝑙
Energy unit: SI unit is Joule: 1 J = 1 kg.m2/s2 1 cal = 4.184 J or 1 J = = 0.239 cal
4.184
1 kJ = 1000 J = 0.239 kcal= 239.0 cal
calorie - energy required to raise the temperature of 1 g of water by 1 C
Calorie – the nutritional Calorie (capital C); the unit that diet tables use to show the energy available from food is
actually a kilocalorie

Heat, q – the energy transferred between a system and its surroundings as a result of a difference in their
temperatures only
*Exothermic - heat is released to surroundings; q < 0 Ex. freezing, condensation
*Endothermic - heat is absorbed from surroundings; q > 0 Ex. melting, boiling
Work, w – involves a change of energy in which a body is moved through a distance, d, against some force, f.
w=fxd

Enthalpy

Enthalpy, ΔH - heat transferred between a system and surroundings during a chemical reaction at constant pressure
*Note: reactions carried out in open containers are carried out at constant P - atmospheric P.

We will consider two situations most commonly encountered in the laboratory; one in which the volume of the system is
kept constant and one in which the pressure applied on the system is kept constant.

At constant volume, ΔV = 0 and no PV work will result from this situation. Therefore, the change in energy, ΔU, will be
calculated as

ΔU = q + w w = −PΔV = 0
ΔU = q − PΔV
ΔU = qv
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where v is added as a subscript to indicate that it is a constant-volume process.

At constant pressure,

ΔU = q + w = −PΔV
ΔU = qp − PΔV
qp = ΔU + PΔV

From this form, we can now define enthalpy (H):

ΔH = ΔU + Δ(PV)

and so, if pressure is held constant,

ΔH = ΔU + PΔV

qp = ΔU = ΔH

An exothermic process results in a decrease in the

enthalpy of the system: Hproducts < Hreactants,
so H < 0.

Exothermic: H < 0, - value

We can consider heat as a product.

CH4(g) + 2O2(g) CO2(g) + 2H2O(g) + heat

An endothermic process results in an increase in the

enthalpy of the system:
Hproducts > Hreactants, so ΔH > 0.

Endothermic: H > 0, + value;

Heat is treated as a reactant.

CO2(g) + 2H2O(g) + heat CH4(g) + 2O2(g)

Take for instance the reversible reaction:

CH4(g) + 2O2(g) ⇋ CO2(g) + 2H2O(g) + heat

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Similarities between H & U:

• H and U are state functions; most of ΔU occurs as heat transfer, so ΔH ≈ ΔU

Heat of Reaction: H = Hproducts - Hreactants

Enthalpy of reaction = heat content of products - heat content of reactants

• Each chemical reaction has an associated H

Ex. 2H2(g) + O2(g) → 2H2O(g) H = - 483.6 kJ  a thermochemical equation

• Or heat can be written as product in an exothermic reaction (reactant for endothermic):

2H2(g) + O2(g) → 2H2O(g) + 483.6 kJ

Characteristics of Enthalpy:
1) Enthalpy is an extensive property - ∆H depends on amount of reactant consumed or product formed.
Ex. 2H2(g) + O2(g) → 2H2O(g) H = - 483.6 kJ
483.6 kJ is released to the surroundings when 2 moles of water form. If 1 mole H2O forms, 241.8 kJ of
heat evolve.
Ex. Calculate the amount of heat evolved when 5.00 g of H2O2 decomposes.

2H2O2(l) → 2 H2O (l) + O2(g) H = -196 kJ

1 𝑚𝑜𝑙 𝐻2 𝑂2 − 196 𝑘𝐽
5.00 𝑔 𝐻2 𝑂2 ( )( ) = -14.4 kJ
34.𝑜 𝑔𝐻2 𝑂2 2 𝑚𝑜𝑙 𝐻2 𝑂2

2) If we write the reverse reaction, the sign of H changes.

Exothermic: 2H2(g) + O2(g) → 2H2O(g) H = -483.6 kJ

Endothermic: 2H2O(g) → 2H2(g) + O2(g) H = 483.6 kJ

3) The enthalpy depends on the physical state of the reactants and products.
H2O(g) → H2O(l) H = - 44 kJ

Calorimetry – an experimental technique that determines the energy change associated with a chemical or physical
process; temperature change is observed when a system releases or absorbs energy in the form of heat

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Calorimeter – a device for measuring the heat released or absorbed by a physical or chemical process

Two common types of calorimeters:

1. Constant- pressure calorimeter - a “coffee-cup” calorimeter

- often used to measure the heat transferred (qp)
in processes open to the atmosphere
- common use is to find the specific heat
capacity of a solid that does not react with or
dissolve in water

heat capacity, C - amount of heat required to raise the temperature by 1 C (or 1 K).
𝑞
𝐶= = in units of J/K ∆𝑇 = Tf - Ti
∆𝑇

specific heat capacity, c - amount of heat required to raise the temperature of 1 gram of a substance by 1 C
(or 1 K). Units: J/gC (or J/gK)
specific heat capacity,
𝑞
c = q = mass x c x ΔT
𝑚 𝑥 ∆𝑇

molar heat capacity, C - heat capacity of 1 mole of a substance. Units: J/molC

• H2O has a high specific heat – it takes a lot of heat to raise the T of water
• metals have low specific heats – only takes a little heat to increase T

How do we find specific heat of a material?

heat lost + heat gained = 0 so, heat lost = - heat gained

Example. A 150.0 g metal is heated to 78.4 C. The metal is placed in 100.0 g H2O at 25.0C. The final temperature of
the mixture is 33.43 C. What is the specific heat of the metal? For H2O, c = 4.18 J/gC.
qmetal = - qwater
mmetalcmetalΔTmetal = - mwatercwaterΔTwater
𝐽
−100.0 𝑔 (4.18 0 )(8.43 0𝐶 )
−𝑚𝑤𝑎𝑡𝑒𝑟 𝑐𝑤𝑎𝑡𝑒𝑟 ∆𝑇𝑤𝑎𝑡𝑒𝑟 𝑔 𝐶 𝐽
Cmetal = = = 0.522 𝑔 0𝐶
𝑚𝑚𝑒𝑡𝑎𝑙 ∆𝑇𝑚𝑒𝑡𝑎𝑙 150.0 𝑔 (−44.97 0𝐶)

For solutions:
qsoln = msoln csoln T
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 For dilute solutions:

csoln = cH2O = 4.18 J/g K

Since calorimeter prevents heat gain or loss to surroundings, heat of the reaction is transferred to the solution:
H = qrxn = - qsoln If temp increases (T is +), reaction is exothermic and qrxn is negative

Example. When a 4.25 g sample of ammonium nitrate dissolves in 60.0 grams of water, the temp. drops from 22.0 C
to 16.9 C. Calculate H in kJ/mol NH4NO3 for the reaction:
NH_4 NO_3 (s) → NH_4^ + (aq) + NO_3^ − (aq)
Assume c = 4.18 J/g 0C
∆H = −msoln csoln ∆T
msoln= 4.25 g + 60.0 g = 64.25 g
J 1 kJ
∆H = −(64.25 g) (4.18 0 ) (16.9 0C − 22.0 0C) = 1370 J ( ) = 1.37 kJ
g C 1000 J
1.37 kJ 80.0 g NH4 NO3 kJ
∆H = ( ) = 25.8
4.25 g NH4 NO3 mol NH4 NO3 mol

2. Constant-volume calorimeter – the bomb calorimeter

- designed to measure very precisely the heat released in a combustion reaction
-qsample = qcalorimeter

The heat of combustion is usually measured

by placing a known mass of a compound in a
steel container called a constant-volume
calorimeter or bomb calorimeter, which is filled
with oxygen at ~30 atm.
The special design of the calorimeter enables
us to assume that it is an isolated system —
no heat or mass is lost to the surroundings.
No heat enters or leaves the system, so the
heat change of the system must be zero. So,

qsystem = qcal + qrxn = 0

− qcal = qrxn
qcal = Ccal Δt

Example. A chemist places one serving of a dessert in a bomb calorimeter and burns it in O 2 (heat capacity of the
calorimeter = 8.151 kJ/K). The temperature increases 4.937 K. Calculate the heat gained by the calorimeter.
qcalorimeter = heat capacity x ΔT = 8.151 kJ/K x 4.937 K = 40.24 KJ

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Example. When 2.50 g of acetylene (C2H2 ) is burned in a bomb calorimeter with a heat capacity of
10.85 kJ/K, the temperature increases from 23.488°C to 34.988°C. What is ΔH (in kJ/mol) for this combustion reaction?

-qrxn = qcal

qcal = Ccal Δt

Δt = (34.988 0C – 23.4880C) = 11.500 0C = 11.500 K

qcal = (10.85 kJ/K ) (11.500 K)

qcal = 124.78 kJ

qrxn 𝑚𝑜𝑙 C2H2

ΔH = - mol C2H2 = 2.50 g C2H2 x = 0.096 mol C2H2
𝑚𝑜𝑙 C2H2 26 𝑔 C2H2

124.78 kJ
ΔH = - = - 1.30 x 10 3 kJ
0.096 𝑚𝑜𝑙C2H2

Example. A 0.500 g sample of naphthalene (C10H8) is burned in a bomb calorimeter containing 650 grams of water an
initial temperature of 20.00 0C. After the reaction, the final temperature of the water is 26.4 0C. The heat capacity of the
calorimeter is 420 J/0C. Calculate the heat of combustion of naphthalene in kJ/mol.

Exercise. A student burns 0.8650 g of graphite, a form of carbon, in a bomb calorimeter, and CO 2 forms. If 393.5 kJ
of heat is released per mole of graphite and T increases 2.613 K, what is the heat capacity of the bomb
calorimeter?

Standard enthalpy of reaction, ΔH0rxn - the enthalpy change for a reaction in which the reactants and products are in
their standard states
for solids and liquids – the standard state is the pure liquid or solid at 1 atm pressure and at a temperature
of interest
for gases – the standard state is the gas at 1 atm

Determination of ΔH0rxn :

A. Using Hess’ Law

Hess' Law of Heat Summation - If a reaction is carried out in a series of steps, then H0rxn for the overall process
must be the sum of the H's for the individual steps.
ΔH0rxn = ΔH0rxn a + ΔH0rxn b + ΔH0rxn c + …
where a, b and c refer to balanced thermochemical equations

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 Calculating ΔH0rxn involves three steps:
1. Identify the target equation, the step whose ΔH0rxn is unknown, and note the no. of moles reactants and
products.
2. Manipulate the equations with known ΔH values so that the target nos. of moles of reactants and products are
on the correct sides. Remember to:
• Change the sign of ΔH when you reverse the equation.
• Multiply numbers of moles and ΔH by the same factor.
3. Add the manipulated equations to obtain the target equation. All substances except those in the target
equation must cancel. Add ΔH values to obtain ΔH0rxn of the overall reaction.

Example

1. Two pollutants that form in automobile exhaust are CO and NO. An environmental chemist
must convert these pollutants to less harmful gases through the following:

1
CO(g) + NO(g) → CO2(g) + N (g)
2
ΔH= ?

Given the following information, calculate the unknown ΔH:

1
CO(g) + O (g) → CO2 (g)
2
ΔH = -283.0 kJ

N2(g) + O2(g) → 2NO(g) ΔH = 180.6 kJ

2. Calculate H0rxn for: 2S(s) + 2 OF2(g) → SO2(g) + SF4(g)

Use the following reactions and enthalpy changes:
OF2 (g) + H2O (l) → O2 (g) + 2 HF(g) ΔH1 = -276.6 kJ
SF4 (g) + 2H2O (l) → SO2 (g) + 4 HF(g) ΔH2 = -827.5 kJ
S(s) + O2 (g) → SO2 (g) ΔH3 = -296.9 kJ
___________________________________________________________________________

2OF2 (g) + 2H2O (l) → 2O2 (g) + 4HF(g) 2ΔH1 = -553.2 kJ

SO2 (g) + 4 HF(g) → SF4 (g) + 2H2O(l) - ΔH2 = +827.5 kJ
2S(s) + 2O2 (g) → 2SO2 (g) 2ΔH3 = -593.8 kJ
___________________________________________________________________________
2S(s) + 2OF2 (g) → SO2 (g) + SF4 (g) ΔH0rxn = -319.5 kJ
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 Exercises:

1. Calculate H0rxn for 2C + 3H2(g) → C2H6(g)

Use the following reactions and enthalpy changes:

2 C2H6(g) + 7O2 → 4CO2(g) + 6H2O(l) ΔH1 = -3120 kJ

C(s) + O2(g) → CO2(g) ΔH2 = -394 kJ
2H2(g) + O2(g) → 2H2O(l) ΔH3 = -572 kJ

2. Calculate the H0rxn for solid Mg(OH)2 given the following reactions. Hint: Write the combination reaction for the
formation of Mg(OH)2from its elements.
2 Mg(s) + O2(g) → 2 MgO(s) ΔH1 = -1203.6 kJ
Mg(OH)2(s) → MgO(s) + H2O(l) ΔH2 = 37.1 kJ
2H2(g) + O2(g) → 2H2O(l) ΔH3 = -571.7 kJ