Introduction to Atomic

and Molecular
Concepts
CHEM1010, 2023
Prof. Alister Page
C222, Chemistry Building
Consultation: Any time!

CHEM1010 Discussion Board (week 1-4)

Email: alister.page@newcastle.edu.au
Chemical Thermodynamics
ΔU, q, w – How Much Heat?

• A chemical reaction will lose heat energy to the surroundings (making them hotter), or gain heat energy
from the surroundings (making them colder).
• Temperature change can be easily measured. But, how do we relate it to the change in internal energy, so
that we can understand something about the ΔU for the reaction?
• We use the heat capacity. The heat capacity is a measure of how much energy must be added to, or
removed from, a certain mass of substance, in order to bring about a temperature change of 1 K (= 1ºC).
• Since enthalpy is measured in J, heat capacity is measured in J/K (= J K-1) – i.e. “Joules per Kelvin”.
• The larger the heat capacity, the larger amount of energy is required to increase/decrease the temperature
of that substance.

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Chemical Thermodynamics
Specific Heat Capacity
• Heat capacity is an example of an extensive property – it depends on how much substance is present.
For example, to heat a teaspoon of water by 1 K, you will need less energy than to heat a swimming
pool by 1 K.
• The specific heat capacity C is the heat capacity per gram of substance:

where
q = quantity of heat transferred by heating or cooling.
m = mass of substance present.
DT = change in temperature (i.e. Tfinal – Tinitial)

• The units of C are J g-1 K-1. C can be determined experimentally – take a known mass of substance,
and measure its temperature change while it absorbs a known amount of heat.
CHEM1010: Introductory Chemistry I 3
Chemical Thermodynamics
Specific Heat Capacity

CHEM1010: Introductory Chemistry I 4

Chemical Thermodynamics
Specific Heat Capacity

• If the specific heat capacity of a substance is known, we are able to use the same equation to
calculate the heat emitted/absorbed by a certain mass of that substance, subject to a change
in temperature:

where

q = quantity of heat transferred by heating or cooling.

m = mass of substance present.

ΔT = change in temperature (i.e. Tfinal – Tinitial)

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 Chemical Thermodynamics
Specific Heat Capacity
Example
How much energy (heat) is needed to heat 250 g of iron from 22 ºC to 325 ºC? The specific heat of iron is 0.45 J g-1
K-1.

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 Chemical Thermodynamics
Molar Heat Capacity

• The specific heat capacity C is also often expressed on a molar basis, instead of on a “per gram” basis.
• To convert specific heat capacity into molar heat capacity, use the molar mass.
Example
What is the molar heat capacity of iron?

CHEM1010: Introductory Chemistry I 8

Chemical Thermodynamics
Specific Heat Capacity – Water

• Water has one of the highest specific heats of any

compound:
• 4.184 J g-1 K-1.
• 75.40 J K-1 mol-1.

• This makes water an excellent material for heating and

cooling purposes.
• Power generation (cooling towers).
• Air conditioning (evaporative cooling).
• Regulates global temperature via oceans.
• Water can be used as a way of calculating energy transfer
into/out of a system, and the specific heats of other materials.
CHEM1010: Introductory Chemistry I 10
 Chemical Thermodynamics
Specific Heat Capacity – Water
Example
A 15.5 g piece of chromium heated to 100.0 ºC is dropped into 55.5 g of water at 16.5 ºC. The final
temperature of both the metal and the water is 18.9 ºC. What is the specific heat of the chromium?

CHEM1010: Introductory Chemistry I 11

Chemical Thermodynamics
Internal Energy (U) & Enthalpy (H)

• The internal energy U consists of all kinetic and potential energies of the system, i.e. due to the
motion and interaction of its atoms and molecules.
• But in reality, the system will exist at a constant pressure, and will occupy a physical volume in
space.

• The energy associated with “making room for the system” (= pV) in the surroundings is NOT
included in U. Including this energy leads us to an improved description of the system’s energy:

H = U + pV

• This new quantity H is known as the enthalpy of the system.

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Chemical Thermodynamics
Internal Energy (U) & Enthalpy (H)

• Enthalpy H, like internal energy U is a state function.

• As for U, H cannot be measured. Only changes in H can be measured.

• For a chemical reaction, the change in enthalpy is defined as

DH = Hproducts – Hreactants

Or,

DH = Hfinal – Hinitial

• When pressure is constant, DH is equivalent to the heat produced/consumed by the reaction.

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Chemical Thermodynamics
Endothermic vs Exothermic

• As for DU, the sign of DH is critical:

• When DH < 0, heat flows from the system to the surroundings.

• When DH < 0 the process is exothermic.
• The surroundings get hotter – i.e. exothermic reactions get hot.

• When DH > 0, heat flows from the surroundings to the system.

• When DH > 0 the process is endothermic.
• The surroundings get colder – i.e. endothermic reactions get
cold.
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Chemical Thermodynamics
Endothermic vs Exothermic
• Example: exothermic reaction

8N2O(g) + 4CS2(g) ➝ S8(s) +4CO2(g) +8N2(g) + energy

The “Barking Dog” reaction

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Chemical Thermodynamics
Endothermic vs Exothermic

• Example: endothermic reaction

Ba(OH)2.8H2O(s) + 2NH4NO3(s) + energy ➝ Ba(NO3)2(aq) + 10H2O(l) + 2NH3(g)

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Chemical Thermodynamics
Enthalpies and Chemical Change

2H2(g) + O2(g) ➝ 2H2O(l) + energy 2H2O(l) + energy ➝ 2H2(g) + O2(g)

DH = -571.2 kJ mol-1 DH = +571.2 kJ mol-1

• What do you notice about these two reactions?

• One released energy, the other requires energy.
• Overall, the energy released by one is MUCH larger than that required by the other.
• The enthalpy of one is the negative of the other.
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Chemical Thermodynamics
Enthalpies and Chemical Change

DrH = Hproducts – Hreactants 2H2O(l)

• The enthalpy of reaction is defined as the difference

in enthalpies of the reaction products and reactants. +571.2 -571.2
kJ mol-1 kJ mol-1
• For any chemical reaction, DrH for the reverse
reaction is the same number as DrH for the forward
reaction, but with the opposite sign. 2H2(g) + O2(g)

• This is the result of reactants becoming products, and

products becoming reactants in the reverse reaction.
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Chemical Thermodynamics
Enthalpies and Chemical Change

2H2(g) + O2(g) ➝ 2H2O(l) + energy 2H2O(l) + energy ➝ 2H2(g) + O2(g)

DH = -571.2 kJ mol-1 DH = +571.2 kJ mol-1

• Enthalpy is an extensive property, just like internal energy U.

• Enthalpies of reaction DrH are also extensive. The more reactant you have, the more enthalpy will be produced/consumed during the
reaction. For example:
• Hindenberg: ~7 x 106 cubic feet ~ 9 x 106 mol. So DrH ~ - 4.3 x 1012 J (~4.3 terajoules)!!

• Beaker: ~100 mL ~ 5.5 mol. So DrH ~ + 2.6 x 106 J (~2.6 megajoules).

CHEM1010: Introductory Chemistry I 21
Chemical Thermodynamics
Enthalpies and Chemical Change

• Consider two reactions that are nearly the same:

CH4(g) + 2O2(g) ➝ CO2(g) + 2H2O(l) DrH = - 890 kJ/mol

CH4(g) + 2O2(g) ➝ CO2(g) + 2H2O(g) DrH = - 802 kJ/mol

• The only difference here is the physical state of the H2O product – liquid water is produced in the 1st reaction, gaseous water in the 2nd.
This leads to a difference of 88 kJ/mol in DrH.
• Where does this difference come from? This can be determined by adding the two reactions together:
CO2(g) + 2H2O(l) ➝ CH4(g) + 2O2(g) DrH = + 890 kJ/mol

CH4(g) + 2O2(g) ➝ CO2(g) + 2H2O(g) DrH = - 802 kJ/mol

2H2O(l) ➝ 2H2O(g) DrH = +88 kJ/mol

• i.e. the difference in DrH corresponds to the enthalpy associated with water vaporising.

• So, this tells us that DrH depends on the physical states of the reactants and products.

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Chemical Thermodynamics
Thermochemical Equations

• A chemical equation accompanied by the DrH value is a thermochemical equation.

• There are 3 basic rules for dealing with thermochemical equations:

1. If the equation is reversed (i.e. reactants become products and vice versa), the sign of DrH must also be
reversed.

2. Substances can only be cancelled on both sides of the arrow if they are in the same state. i.e. DrH
depends on the physical state of all reactants and products.

3. If all the coefficients of an equation are multiplied or divided by the same factor, the value of DrH must
also be multiplied or divided by that factor. i.e. DrH is an extensive property.

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