Page 1: Introduction to Thermochemistry

What is Thermochemistry?
Thermochemistry is the study of heat and its relationship to chemical reactions or physical
changes of state. It's a branch of thermodynamics, which deals with energy transformations.
Key Definitions:
●​ Energy (U or E): The capacity to do work or produce heat. It can exist in various forms,
including kinetic energy (energy of motion) and potential energy (energy of position or
composition). The SI unit of energy is the joule (J).
●​ Heat (q): The transfer of energy between two objects due to a temperature difference.
Heat always flows from a hotter object to a colder one.
●​ Work (w): Energy transferred when a force acts on an object and causes it to move. In
chemistry, pressure-volume work (P-V work) is common, such as the work done by a
gas expanding against a pressure.
●​ System and Surroundings:
○​ System: The part of the universe we are interested in (e.g., a chemical reaction in
a test tube).
○​ Surroundings: Everything outside the system.
●​ Internal Energy (U or E): The total energy of a system, including the kinetic and
potential energies of all its particles. It's a state function, meaning it only depends on
the current state of the system, not on how it got to that state. We cannot measure the
absolute value of internal energy, but we can measure changes in internal energy (ΔU or
ΔE).
The First Law of Thermodynamics:
This fundamental law states that energy cannot be created or destroyed; it can only be
converted from one form to another. In other words, the total energy of the universe is
constant.
Mathematically, the first law is expressed as:
ΔU=q+w
Where:
●​ ΔU is the change in internal energy of the system.
●​ q is the heat added to the system (positive) or released by the system (negative).
●​ w is the work done on the system (positive) or by the system (negative).
State Functions:
A state function is a property that depends only on the current state of the system, not on the
path taken to reach that state. Internal energy (U), enthalpy (H - discussed later), and
temperature (T) are state functions. Heat (q) and work (w) are not state functions; their values
depend on the path of the process.
Page 2: Enthalpy and Thermochemical Equations

Enthalpy (H):
Enthalpy is a thermodynamic property defined as:
H=U+PV
Where:
●​ H is enthalpy
●​ U is internal energy
●​ P is pressure
●​ V is volume
For reactions carried out at constant pressure (which is very common in chemistry), the
change in enthalpy (ΔH) is equal to the heat transferred between the system and the
surroundings:
ΔH=qp​
Enthalpy, like internal energy, is a state function.
Enthalpy Change (ΔH):
The enthalpy change (ΔH) is the heat absorbed or released by a system during a process at
constant pressure.
●​ Exothermic Reactions: Reactions that release heat to the surroundings (ΔH<0). The
products have lower enthalpy than the reactants.
●​ Endothermic Reactions: Reactions that absorb heat from the surroundings (ΔH>0).
The products have higher enthalpy than the reactants.
Thermochemical Equations:
A thermochemical equation is a balanced chemical equation that includes the enthalpy
change (ΔH) for the reaction. Key points:
●​ The physical states of all reactants and products (s, l, g, aq) must be specified because
they affect the enthalpy change.
●​ The coefficients in the balanced equation represent moles, not individual molecules.
●​ The enthalpy change (ΔH) is usually written at the end of the equation.
●​ The sign of ΔH indicates whether the reaction is exothermic (-) or endothermic (+).
●​ If the equation is multiplied by a factor, ΔH is also multiplied by the same factor.
●​ If the equation is reversed, the sign of ΔH is reversed.
Example:
2H2​(g)+O2​(g)⟶2H2​O(l)ΔH=−571.6 kJ
This equation tells us that when 2 moles of hydrogen gas react with 1 mole of oxygen gas to
produce 2 moles of liquid water, 571.6 kJ of heat is released (exothermic).
Page 3: Hess's Law

Hess's Law:
Hess's Law states that the enthalpy change for a reaction is independent of the path taken; it
only depends on the initial and final states. In other words, if a reaction can be carried out in a
series of steps, the sum of the enthalpy changes for each step will equal the enthalpy change
for the overall reaction.
This law is based on the fact that enthalpy is a state function.
Using Hess's Law:
Hess's Law allows us to calculate enthalpy changes for reactions that are difficult or
impossible to measure directly. We can use known enthalpy changes of other reactions to
determine the desired ΔH.
Steps Involved:
1.​ Identify the target reaction (the reaction whose ΔH you want to find).
2.​ Arrange the given reactions (whose ΔH values are known) so that, when added
together, they give the target reaction. This may involve:
○​ Reversing reactions (change the sign of ΔH).
○​ Multiplying reactions by coefficients (multiply ΔH by the same factor).
3.​ Add the manipulated reactions and their corresponding ΔH values. The enthalpy change
of the target reaction is the sum of the ΔH values of the steps.
Example:
Calculate ΔH for the reaction:
C(s)+2H2​(g)⟶CH4​(g)
Given:
1.​ C(s)+O2​(g)⟶CO2​(g)ΔH1​=−393.5 kJ
2.​ H2​(g)+21​O2​(g)⟶H2​O(l)ΔH2​=−285.8 kJ
3.​ CO2​(g)+2H2​O(l)⟶CH4​(g)+2O2​(g)ΔH3​=+890.3 kJ
Solution:
1.​ Target reaction: C(s)+2H2​(g)⟶CH4​(g)
2.​ Manipulate given reactions:
○​ Reaction 1: Leave as is: C(s)+O2​(g)⟶CO2​(g)ΔH1​=−393.5 kJ
○​ Reaction 2: Multiply by 2: 2H2​(g)+O2​(g)⟶2H2​O(l)2ΔH2​=−571.6 kJ
○​ Reaction 3: Reverse: CH4​(g)+2O2​(g)⟶CO2​(g)+2H2​O(l)−ΔH3​=−890.3 kJ
3.​ Add the manipulated reactions:​
C(s)+O2​(g)⟶CO2​(g)ΔH1​=−393.5 kJ
2H2​(g)+O2​(g)⟶2H2​O(l)2ΔH2​=−571.6 kJ
CH4​(g)+2O2​(g)⟶CO2​(g)+2H2​O(l)−ΔH3​=−890.3 kJ​
C(s)+2H2​(g)⟶CH4​(g)ΔH=ΔH1​+2ΔH2​−ΔH3​=−74.8 k
J
Page 4: Standard Enthalpies of Formation

Standard State:
The standard state of a substance is a specified set of conditions used for comparing
thermodynamic properties. The standard state is defined as:
●​ For a gas: 1 atm (101.325 kPa) pressure.
●​ For a liquid or solid: The pure substance at 1 atm pressure.
●​ For a solution: 1 M concentration.
The standard temperature is usually, but not always, specified as 298 K (25 °C).
Standard Enthalpy of Formation (ΔHf∘​):
The standard enthalpy of formation of a compound is the enthalpy change when one mole of
the compound is formed from its elements in their standard states. The symbol ΔHf∘​is used
to represent it.
●​ The standard enthalpy of formation of any element in its most stable form at standard
conditions is zero. For example, ΔHf∘​(O2​(g))=0, ΔHf∘​(C(graphite))=0.
Using ΔHf∘​to Calculate Standard Enthalpy Change of Reaction (ΔHrxn∘​):
The standard enthalpy change of a reaction can be calculated using the standard enthalpies
of formation of the reactants and products:
ΔHrxn∘​=∑nΔHf∘​(products)−∑mΔHf∘​(reactants)
Where:
●​ ΔHrxn∘​is the standard enthalpy change of the reaction.
●​ n and m are the stoichiometric coefficients of the products and reactants, respectively,
from the balanced chemical equation.
●​ ΔHf∘​is the standard enthalpy of formation.
Example:
Calculate ΔHrxn∘​for the following reaction:
2H2​O2​(l)⟶2H2​O(l)+O2​(g)
Given:
●​ ΔHf∘​(H2​O2​(l))=−187.6 kJ/mol
●​ ΔHf∘​(H2​O(l))=−285.8 kJ/mol
●​ ΔHf∘​(O2​(g))=0 kJ/mol
Solution:
ΔHrxn∘​=[2ΔHf∘​(H2​O(l))+ΔHf∘​(O2​(g))]−[2ΔHf∘​(H2​O2​(l))]ΔHrxn∘​=[2(−285.8 kJ/mol)+0]−[2(−187.
6 kJ/mol)]ΔHrxn∘​=−571.6 kJ/mol+375.2 kJ/mol=−196.4 kJ
Page 5: Calorimetry

Calorimetry:
Calorimetry is the experimental technique used to measure the heat changes associated with
chemical reactions or physical changes. A calorimeter is a device used to measure these heat
changes.
Types of Calorimeters:
●​ Constant-Volume Calorimeter (Bomb Calorimeter): Used to measure the heat of
combustion reactions. The reaction is carried out in a sealed, rigid container (the
"bomb") at constant volume. The heat absorbed or released by the reaction is
transferred to the surrounding water, and the temperature change of the water is
measured. Since volume is constant, qv​=ΔU.
●​ Constant-Pressure Calorimeter (Coffee Cup Calorimeter): A simple calorimeter
made of nested Styrofoam cups, used for measuring heat changes in solutions (e.g.,
neutralization reactions, dissolution processes). The reaction occurs at constant
pressure (atmospheric pressure). The heat absorbed or released by the reaction causes
a temperature change in the solution, which is measured. Here, qp​=ΔH.
Calculations in Calorimetry:
The heat absorbed or released by the calorimeter and its contents (usually water) is
calculated using the following equation:
q=mcΔT
Where:
●​ q is the heat absorbed or released (in joules or kilojoules).
●​ m is the mass of the substance that undergoes the temperature change (usually the
mass of the water in the calorimeter) (in grams).
●​ c is the specific heat capacity of the substance (the amount of heat required to raise
the temperature of 1 gram of the substance by 1 degree Celsius) (in J/g°C or kJ/kg°C).
●​ ΔT is the change in temperature (in °C or K).
Important Considerations:
●​ The heat absorbed by the calorimeter itself must be accounted for. This is done using
the calorimeter constant (C), which is the heat capacity of the calorimeter (in J/°C or
kJ/°C).
●​ For a bomb calorimeter (constant volume): qrxn​=−qcalorimeter​=−Ccal​ΔT
●​ For a coffee cup calorimeter (constant pressure): qrxn​=−qsolution​=−mcsoln​ΔT
●​ The negative sign indicates that if the reaction releases heat (exothermic), the water
absorbs heat, and vice versa.
Example:
When 1.00 g of sucrose (C12​H22​O11​) is burned in a bomb calorimeter, the temperature of the
water increases from 24.92 °C to 28.33 °C. The calorimeter contains 2000 g of water, and the
heat capacity of the bomb is 430 J/°C. Calculate the heat of combustion of sucrose (in
kJ/mol).
Solution:
1.​ Calculate ΔT: ΔT=28.33°C−24.92°C=3.41°C
2.​ Calculate heat absorbed by water:
qwater​=mcΔT=(2000 g)(4.184 J/g°C)(3.41°C)=28500 J=28.5 kJ
3.​ Calculate heat absorbed by the bomb:
qbomb​=Ccal​ΔT=(430 J/°C)(3.41°C)=1470 J=1.47 kJ
4.​ Total heat released by the combustion:
qrxn​=−(qwater​+qbomb​)=−(28.5 kJ+1.47 kJ)=−29.97 kJ
5.​ Calculate moles of sucrose: n=342.3 g/mol1.00 g​=0.00292 mol
6.​ Calculate heat of combustion per mole: 0.00292 mol−29.97 kJ​=−10260 kJ/mol
The heat of combustion of sucrose is -10260 kJ/mol.