This handout is prepared by the faculty of the Chemistry Department, College of Science and Mathematics, MSU- Iligan Institute

of Technology.  
 
THERMOCHEMISTRY
Energy Flow and Chemical Change

Thermochemistry is a branch of thermodynamics no matter is exchanged with the surroundings, but

which focuses on the relationships between chemical when igniting the fuse to burn the sample under study,
reactions and energy changes that involve heat. energy must travel into the system

Thermodynamics deals with the study of energy and Isolated System

its transformations. In an isolated system, neither matter nor energy can
pass between the system and surroundings.
THE SYSTEM AND ITS SURROUNDINGS
These systems are purely theoretical, as there is
In a thermodynamic analysis, the system is the subject always some energy exchange with systems and
of the investigation. It is simply something a scientist surroundings.
is interested in studying. A system is a region
containing energy and/or matter that is separated STATE FUNCTIONS AND
from its surroundings by arbitrarily imposed walls or THE PATH INDEPENDENCE OF THE ENERGY
boundaries. CHANGE
The surroundings are everything outside the system state function
and are the place where the observation and a property dependent only on the current state of the
measurements of the system are taken. system, its composition, volume, pressure, and
A boundary is a closed surface surrounding a system temperature
through which energy and mass may enter or leave the examples: E, P, V
system. state functions do not depend on the path the
•  
example: a chemist may be studying the amount of system took to reach that state
heat evolved or released during a reaction in a beaker •   state functions do not depend on how the
system: the solution contained in the beaker change takes place
surroundings: beaker and everything else, including the •   the current state depends only on the
lab where the chemist takes measurements difference between the final and initial states
boundary: walls of the beaker that separates the ΔE , ΔP , ΔV
solution from the rest of the universe path functions
path functions depend on how the change takes place
The system and the surroundings combined are path functions depend on the path the system took to
essentially "everything". reach the final state from the initial state
This is because the combined energy in the system and examples: q, w
the surroundings is a constant.
Energy can flow between these two, but the total ENERGY FLOW TO AND FROM A SYSTEM
energy is constant.
Therefore, internal energy, E, of a system is the sum of all the
system + surroundings = universe potential and kinetic energies for all the particles in
the system
E = ∑Ekinetics + ∑Epotential
TYPES OF SYSTEMS
Open System When a chemical system changes from reactants to
In an open system, both matter and energy (heat) can products and the products return to the starting
be exchanged between the system and its temperature, the internal energy has changed.
surroundings. To determine this change, ΔE, we measure the
example: machines, such as cars difference between the system’s internal energy after
both energy and matter can be exchanged between the the change (Efinal) and before the change (E initial):

car (the system) and its surroundings in the form of ΔEsystem = Efinal ― Einitial
heat (energy) and gasoline (matter) For a chemical reaction,
Closed System ΔEsystem = Eproducts ― Ereactants
In a closed system, only energy can be exchanged Because the total energy must be conserved, a change
between the system and its surroundings, no matter in the energy of the system is always accompanied by
can transfer between the two. an opposite change in the energy of the surroundings.
example: bomb calorimeter

 
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This handout is prepared by the faculty of the Chemistry Department, College of Science and Mathematics, MSU- Iligan Institute of Technology.  
 
Two ways in which a system can change its internal (surroundings) because the surroundings have a lower
energy: temperature
1. by losing some energy to the surroundings all other forms of energy transfer (mechanical,
Efinal < Einitial electrical, etc.) involve some type of work

ΔE < 0 (exothermic reaction) work, w

the energy transferred when an object is moved by a
energy diagrams for the transfer of internal energy force
(E) between a system and its surroundings example: when a player (system) kick a football
(surroundings), energy is transferred as work to move
the ball

The total change in a system’s internal energy is the

sum of the energy transferred as heat and/or work.
ΔE = q + w
the numerical values of q, w and ΔE can be either
positive or negative depending on the change the
system undergoes
•   energy coming into the system is positive
•   energy going out from the system is negative

2. by gaining some energy from the surroundings

Efinal > Einitial
ΔE > 0 (endothermic reaction)

energy diagrams for the transfer of internal energy

(E) between a system and its surroundings * For q à (+) means system gains heat; (‒) means
system loses heat
For w à (+) means work done on the system; (‒) means
work done by the system.

note:
change in energy is always energy transfer
from system to surroundings or
from surroundings to system

HEAT AND WORK: TWO FORMS OF ENERGY

FIRST LAW OF THERMODYNAMICS
TRANSFER
THE LAW OF ENERGY CONSERVATION
heat or thermal energy, q
the energy transferred between a system and its The total energy of the universe is constant.
surroundings as a result of a difference in their When a system gains energy, the surroundings lose it.
temperatures When a system loses energy, the surroundings gain it.
example: energy in the form of heat is transferred Energy can be converted from one form to another.
from hot soup (system) to the bowl, air, and table Energy cannot be created or destroyed.
Energy is always conserved.

 
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This handout is prepared by the faculty of the Chemistry Department, College of Science and Mathematics, MSU- Iligan Institute of Technology.  
 
The energy of the system plus the energy of the
surroundings remains constant.

A mathematical expression of the first law

ΔEuniverse = ΔEsystem + ΔEsurroundings = 0

Units of Energy:
2 2
Joule (J) 1 J = 1 kg m /s
calorie (cal) 1 cal = 4.184 J
Calorie (Cal) 1 Cal = 1000 cal
British Thermal Unit (BTU) 1 BTU = 1055 J

Sample Problem 1: Determining the Change in

Internal Energy of a System
When gasoline burns in a car engine, the heat released
causes the products CO2 and H2O to expand, which
pushes the pistons outward. Excess heat is removed
by the car’s cooling system. If the expanding gases do
451 J of work on the pistons and the system loses 325
The Meaning of Enthalpy: H
J to the surroundings as heat, calculate the change in
energy (DE) in J, kJ, and kcal.
H = E + PV ΔH = ΔE + PΔV
(-0.776 kJ; -0.185 kcal)
ΔE = q + w w = ‒ PΔV
ΔE = q ‒ PΔV
at constant pressure, q = qp
ENTHALPY
ΔE = qp ‒ PΔV
HEATS OF REACTION AND CHEMICAL CHANGE
by rearrangement
ΔE = q + w qp = ΔE + PΔV
two most important types of chemical work: therefore,
electrical work - the work done by moving charged qp = ΔH
particles Thus, the change in enthalpy equals the heat gained
PV work - the work done by an expanding gas or lost at constant pressure.
when a gas expands, work is done on the surroundings With most changes occurring at constant pressure, ΔH
so it has a negative sign because the system loses is more relevant than ΔE and easier to find:
energy to find ΔH, measure qp.
w = ‒ PΔV
COMPARING ΔE AND ΔH
Pressure - Volume Work Knowing the enthalpy change of a system tells a lot
When the volume (V) of a system increases by an about its energy change. In fact, because many
amount ΔV against an external pressure (P), the system reactions involve little, if any, PV work, most or all of
pushes back, and thus does PV work on the the energy change occurs as a transfer of heat.
surroundings Consider these three cases:
1. Reactions that do not involve gases.
ΔH ≈ ΔE
2 KOH (aq) + H2SO4 (aq) → K2SO4 (aq) + 2H2O (l)
liquids and solids undergo very small volume changes
ΔV ≈ 0 PΔV ≈ 0 ΔH ≈ ΔE
2. Reactions in which the number of moles of gas does
not change.
ΔH = ΔE
N2 (g) + O2 (g) → 2NO (g)
when the total amount of gaseous reactants equals the
total amount of gaseous products
ΔV = 0 PΔV = 0 ΔH = ΔE

 
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This handout is prepared by the faculty of the Chemistry Department, College of Science and Mathematics, MSU- Iligan Institute of Technology.  
 
3. Reactions in which the number of moles of gas does Enthalpy Diagram for Endothermic Processes
change but q is >>> PΔV.
heat + H2O(s) H2O(l)
ΔH ≈ ΔE
2H2 (g) + O2 (g) → 2H2O (g)
ΔH = ‒ 483.6 kJ PΔV = ‒ 2.5 kJ
ΔE = ΔH ‒ PΔV
ΔE = ‒ 483.6 kJ ‒ (‒2.5 kJ) = ‒ 481.1 kJ
most of ΔE occurs as heat transfer, so ΔH ≈ ΔE

EXOTHERMIC AND ENDOTHERMIC PROCESSES

Because E, P, and V are state functions, H is also a

state function, which means that ΔH depends only on Ice melts with an increase in enthalpy because heat
the difference between Hfinal and Hinitial. enters the system.

The enthalpy change of a reaction, also called the

Sample Problem 2: Drawing Enthalpy Diagrams and
heat of reaction, ΔHrxn, always refers to Hfinal minus
Determining the Sign of ΔH
Hinitial :
In each of the following cases, determine the sign of
ΔH = Hfinal - Hinitial ΔH, state whether the reaction is exothermic or
endothermic, and draw an enthalpy diagram.
ΔH = Hproducts - Hreactants
(a) H2(g) + 1/2O2(g) ⎯→ H2O(l) + 285.8kJ
Therefore, because Hproducts can be either more than (b) 40.7kJ + H2O(l) ⎯→ H2O(g)
or less than Hreactants, the sign of ΔH indicates whether
heat is absorbed or released in the chemical change or SOME IMPORTANT TYPES OF ENTHALPY CHANGE
chemical reaction. •   When 1 mol of a compound is burned, the heat
We determine the sign of ΔH by imagining the heat of reaction is called the heat of combustion
as a “reactant” or “product.” (ΔHcomb) : ΔHrxn = ΔHcomb
An exothermic (“heat out”) process releases heat and C4H10(l) + 13/2 O2(g) ⎯→ 4 CO2(g) + 5 H2O(g)
results in a decrease in the enthalpy of the system.
•   When 1 mol of a compound is produced from its
Exothermic: Hproducts < Hreactants ΔH < 0 elements, the heat of reaction is called the
heat of formation (ΔHf) : ΔHrxn = ΔHf
CH4(g) + 2O2(g) ⎯→ CO2(g) + 2H2O(g) + heat
K(s) + ½ Br2(l) ⎯→ KBr(s)

An endothermic (“heat in”) process absorbs heat and •   When 1 mol of a substance melts, the enthalpy
results in an increase in the enthalpy of the system. change is called the heat of fusion (ΔHfus):

Endothermic: Hproducts > Hreactants ΔH > 0 ΔHrxn = ΔHfus

NaCl(s) ⎯→ NaCl(l)
heat + H2O(s) ⎯→ 2H2O(l)
•   When 1 mol of a substance vaporizes, the
In general, the value of an enthalpy change refers to enthalpy change is called the heat of
reactants and products at the same temperature. vaporization (ΔHvap) : ΔHrxn = ΔHvap
C6H6(l) ⎯→ C6H6(g)
Enthalpy Diagram for Exothermic Processes

CH4(g) + 2O2(g) CO2(g) + 2H2O(g) + heat CALORIMETRY: LABORATORY MEASUREMENT

OF HEATS OF REACTION, ΔHrxn
Data about energy content and use are everywhere—
the calories per serving of a slice of bread, the energy
efficiency rating of a washing machine, the gas mileage
of a new car, the energy content of a teaspoon of sugar
and so forth. How do we measure the heat released or
absorbed by these changes?

The value of ΔHrxn can be determined experimentally

by measuring the heat flow accompanying a reaction at
Methane burns with a decrease in enthalpy because constant pressure. The magnitude of the heat flow
heat leaves the system. can be determined by measuring the magnitude of the
 
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This handout is prepared by the faculty of the Chemistry Department, College of Science and Mathematics, MSU- Iligan Institute of Technology.  
 
temperature change the heat flow produces. The
Specific Heat Capacities of Some Elements,
measurement of the heat flow is calorimetry and the
Compounds, and Materials at 298 K or 25°C.
calorimeter is a device used to measure the heat flow.

To measure qP, which is equal to ΔH, we construct

“surroundings” that retain the heat, and we observe
the temperature change. Then, we relate the quantity
of heat released or absorbed to that temperature
change through a physical property called the specific
heat capacity.

Specific Heat Capacity

The more an object is heated, the higher its
temperature; that is, the quantity of heat (q) absorbed
by an object is proportional to its temperature change:
q ∝ ΔT
The quantity of heat required for an object to change
its temperature by 1 K is called its heat capacity. Heat
capacity is the proportionality constant in the
preceding equation:
q = constant x ΔT

q / ΔT = constant

heat capacity = q / ΔT (in units of J/K)

The specific heat capacity (c) is the quantity of heat

required to change the temperature of 1 gram of a
substance by 1 K.
Note: Some texts use the term specific heat in place
Sample Problem 3: Finding Quantity of Heat from
of specific heat capacity. This usage is very common
Specific Heat Capacity
but somewhat incorrect. Specific heat is the ratio of
A layer of copper welded to the bottom of a skillet
the heat capacity of 1 g of a substance to the heat
weighs 125 g. How much heat is needed to raise the
capacity of 1 g of H2O and therefore has no units.  
temperature of the copper layer from 25°C to 300.°C?
specific heat capacity (c) = q / (mass x ΔT) The specific heat capacity (c) of Cu is 0.387 J/g K.
(in units of J/g K)
The specific heat capacity of liquid water is 4.184 J/g K. The Practice of Calorimetry
The calorimeter is a device used to measure the heat
If the specific heat capacity, c, of the substance being
released or absorbed by a physical or chemical
heated or cooled is known, the mass of the substance
process. This apparatus is the “surroundings” that
and the temperature change can be measured and the
changes temperature when heat is transferred to or
heat absorbed or released can be calculated:
from the system. The two common types of
q = c x mass x ΔT
calorimeters are the constant-pressure calorimeters
Note: and the constant-volume calorimeters.
When an object gets hotter, ΔT is positive. The
object gains heat, so q > 0. Constant-Pressure Calorimetry
When an object gets cooler, ΔT is negative because A “coffee-cup” calorimeter is often used to measure
heat is lost, so q < 0. the heat transferred (qp) in processes open to the
atmosphere. One common use is to find the specific
The molar heat capacity (C), of a substance is the
heat capacity of a solid that does not react with or
quantity of heat required to change the temperature
dissolve in water. The solid (system) is weighed,
of 1 mole of a substance by 1 K:
heated to some known temperature, and added to a
molar heat capacity (C) = q / (moles x ΔT) sample of water (surroundings) of known temperature
(in units of J/mol K) and mass in the calorimeter. With stirring, the final
The specific heat capacity of liquid water is 4.184 J/g water temperature, which is also the final
K so its molar heat capacity is temperature of the solid, is measured.

C of H2O(l) = 4.184 J/g K x 18.02 g/mol

= 75.40 J/mol K
 
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This handout is prepared by the faculty of the Chemistry Department, College of Science and Mathematics, MSU- Iligan Institute of Technology.  
 
The heat lost by the system ( ‒ qsys or ‒ qsolid ) is heat released in a combustion reaction. Combustion
equal in magnitude but opposite in sign to the heat reactions are most accurately studied using a bomb
gained by the surroundings ( + qsurr or qH2O): calorimeter.

‒ qsolid = qH2O
In the bomb calorimeter, the substance to be studied
by substitution
is placed in a small cup within an insulated sealed vessel
called a bomb. The bomb, which is designed to
withstand high pressures, has an inlet valve for adding
by rearrangement oxygen and electrical leads. After the sample has been
placed in the bomb, the bomb is sealed and pressurized
with oxygen. It is then placed in the calorimeter and
covered with an accurately measured quantity of
water. The combustion reaction is initiated by passing
an electrical current through a fine wire in contact
with the sample.
When the wire becomes sufficiently hot, the sample
ignites. The heat released when combustion occurs is
absorbed by the water and the various components of
the calorimeter (which all together make up the
surroundings), causing the water temperature to rise.
The change in water temperature caused by the
reaction is measured very precisely.

Coffee-cup calorimeter. This apparatus is used to

measure the heat at constant pressure (qP).

Sample Problem 4: Finding Specific Heat capacity

A 25.64-g solid in a test tube was heated to 100.00 ⁰ C
and was carefully added to 50.00 g of water in a
coffee-cup calorimeter. The water temperature
changes from 25.10 ⁰ C to 28.49 ⁰ C. Find the specific
Bomb calorimeter. This device (not drawn to scale) is
heat capacity of the solid.
used to measure very precisely the heat released in a
combustion reaction at constant volume (qV).
Sample Problem 5: Relating Heat, Temperature
Change, and Heat Capacity The figure depicts the preweighed combustible sample
(a) How much heat is needed to warm 250 g of water in a metal-walled chamber (the bomb), which is filled
(about 1 cup) from 22 °C (about room temperature) to with oxygen gas and immersed in an insulated water
98 °C (near its boiling point)? (b) What is the molar bath fitted with motorized stirrer and thermometer.
heat capacity of water? A heating coil connected to an electrical source ignites
the sample, and the heat evolved raises the
Constant-Volume Calorimetry temperature of the bomb, water, and other
In the coffee-cup calorimeter, we assume all the heat calorimeter parts. Because the mass of the sample and
is gained by the water, but some must be gained by the the heat capacity of the entire calorimeter is known,
stirrer, thermometer, and other components of the the heat released can be calculated using the
calorimeter. For more precise work, as in constant- measured ΔT.
volume calorimetry, the heat capacity of the entire
calorimeter must be known.
One type of constant-volume apparatus is the “bomb
calorimeter”, designed to measure very precisely the
 
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This handout is prepared by the faculty of the Chemistry Department, College of Science and Mathematics, MSU- Iligan Institute of Technology.  
 
STOICHIOMETRY OF
THERMOCHEMICAL EQUATIONS

A thermochemical equation is a balanced equation that

includes the heat of reaction (ΔHrxn). Note that the
ΔHrxn value shown refers to the amounts (moles) of Sample Problem 6: Using the Heat of Reaction
substances and their states of matter in that (ΔHrxn) to Find Amounts
specific equation. The major source of aluminum in the world is bauxite
The enthalpy change of any process has two aspects: (mostly aluminum oxide). Its thermal decomposition
1. Sign can be represented by
The sign of ΔH depends on whether the reaction is Al2O3(s) ⎯→ 2Al(s) + 3/2O2(g) ΔHrxn = 1676 kJ
exothermic (‒) or endothermic (+). If aluminum is produced this way, how many grams of
A forward reaction has the opposite sign of the aluminum can form when 1.000 x 103 kJ of heat is
reverse reaction. transferred? Al = 26.98 g/mol
Illustration
Decomposition of 2 mol of water to its elements Guidelines when using thermochemical equations:
(endothermic): 1. Enthalpy is an extensive property.
The magnitude of ΔH is proportional to the amount of
reactant consumed in the process.
Formation of 2 mol of water from its elements e.g. 890 kJ of heat is produced when 1 mol of CH4 is
(exothermic): burned in a constant-pressure system:
CH4(g) + 2O2(g) ⎯→ CO2(g) + 2H2O(l) ΔH = ‒890 kJ
2. Magnitude
2. The enthalpy change for a reaction is equal in
The magnitude of ΔH is proportional to the amount of
magnitude, but opposite in sign, to ΔH for the reverse
substance reacting.
reaction.
Illustration
e.g. ΔH for the reverse of the above equation
Formation of 2 mol of water from its elements:
CO2(g) + 2H2O(l) ⎯→ CH4(g) + 2O2(g) ΔH = +890 kJ

Formation of 1 mol of water from its elements:
In thermochemical equations, we often use fractional
coefficients to specify the magnitude of ΔHrxn for a
particular amount of substance. In a particular
reaction, a certain amount of substance is
thermochemically equivalent to a certain quantity of
energy.
In the reaction just shown,
Just as we use stoichiometrically equivalent molar
ratios to find amounts of substances, we use
thermochemically equivalent quantities to find the
heat of reaction for a given amount of substance.
Just as we use molar mass (in g/mol of substance) to
convert moles of a substance to grams, we use the heat
of reaction (in kJ/mol of substance) to convert moles
of a substance to an equivalent quantity of heat (in kJ).
Summary of the relationship between amount (mol) of
substance and the heat (kJ) transferred during a
reaction.
3. The enthalpy change for a reaction depends on the
states of the reactants and products.
CH4(g) + 2O2(g) ⎯→ CO2(g) + 2H2O(l) ΔH = ‒890 kJ
CH4(g) + 2O2(g) ⎯→ CO2(g) + 2H2O(g) ΔH = ‒802 kJ
Less heat would be available for transfer to the
surroundings because the enthalpy of H2O(g) is
greater than that of H2O(l).
Thus, it is important to specify the states of the
reactants and products in thermochemical equations.
In addition, we will generally assume that the
reactants and products are both at the same
temperature, 25 °C, unless otherwise indicated.
HESS’S LAW OF HEAT SUMMATION
Enthalpy is a state function, therefore the enthalpy
change, ΔH, associated with any chemical process
depends only on the amount of matter that undergoes
change and on the nature of the initial state of the
reactants and the final state of the products. This
means that whether a particular reaction is carried out
in one step or in a series of steps, the sum of the
enthalpy changes associated with the individual steps
must be the same as the enthalpy change associated
with the one-step process.

 
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This handout is prepared by the faculty of the Chemistry Department, College of Science and Mathematics, MSU- Iligan Institute of Technology.
This application is based on the Hess’s Law of Heat
Summation which states that if a reaction is carried
out in a series of steps, ΔH for the overall reaction
equals the sum of the enthalpy changes for the
individual steps. This can be restated as the enthalpy
change of an overall process is the sum of the
enthalpy changes of its individual steps.
 
The overall enthalpy change for the process is
independent of the number of steps and independent
of the path by which the reaction is carried out. This
law is a consequence of the fact that enthalpy is a
state function. We can therefore calculate ΔH for any
process as long as we find a route for which ΔH is
known for each step. This means that a relatively small
number of experimental measurements can be used to
calculate ΔH for a vast number of reactions.
To use Hess’s law, we imagine an overall reaction as the
sum of a series of reaction steps, whether or not it
really occurs that way. Each step is chosen because
its ΔH is known. Because the overall ΔH depends only
on the initial and final states, Hess’s law says that we
add together the known ΔH values for the steps to
get the unknown ΔH of the overall reaction.
Similarly, if we know the ΔH values for the overall
reaction and all but one of the steps, we can find the
unknown ΔH of that step.
Hess’s law provides a useful means of calculating
energy changes that are difficult to measure directly.
Illustration
The oxidation of sulfur to sulfur trioxide is the central
process in the industrial production of sulfuric acid
and in the formation of acid rain.
S(s) + 3/2 O2(g) ⎯→ SO3(g)
Determine the ΔH of the oxidation reaction, given the
following thermochemical equations:
S(s) + O2(g) ⎯→ SO2(g) ΔH = ‒296.8 kJ
2SO2(g) + O2(g) ⎯→ 2SO3(g)
Steps involved in calculating ΔH of an unknown :
1. Identify the target equation, the step whose ΔH is
unknown, and note the number of moles of each
reactant and product.
2. Manipulate the equations with known ΔH values so
that the target numbers of moles of reactants and
products are on the correct sides.
Remember to:
• Change the sign of ΔH when you reverse an 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 their ΔH values to obtain
the unknown ΔH.
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Sample Problem 7: Using Hess’s Law to Calculate
an Unknown ΔH
Two gaseous pollutants that form in auto exhaust are
CO and NO. An environmental chemist is studying ways
to convert them to less harmful gases through the
following equation:
CO(g) + NO(g) ⎯→ CO2(g) + 1/2N2(g) ΔH = ?
Given the following information, calculate the unknown
ΔH:
CO(g) + 1/2O2(g) ⎯→ CO2(g) ΔH = -283.0 kJ
N2(g) + O2(g) ⎯→ 2NO(g) ΔH = 180.6 kJ
STANDARD HEATS OF REACTION (ΔHrxn)
The magnitude of any enthalpy change depends on the
temperature, pressure, and state (gas, liquid, or solid
crystalline form) of the reactants and products. To
compare enthalpies of different reactions, we must
define a set of conditions, called a standard state, at
which most enthalpies are tabulated.
The standard state of a substance is its pure form at
atmospheric pressure (1 atm) and the temperature of
interest, which we usually choose to be 298 K (25 °C).
The standard enthalpy change of a reaction is
defined as the enthalpy change when all reactants
and products are in their standard states. We
denote a standard enthalpy change as ΔH°, where the
superscript ° indicates standard-state conditions.
Thermodynamic variables, such as ΔH, vary somewhat
with conditions. Thus, to use heats of reaction and
other thermodynamic data, chemists have established
standard states which is a set of specified conditions
and concentrations:
• For a gas, the standard state is 1 atm with the gas
behaving ideally.
• For a substance in aqueous solution, the standard
state is 1 M concentration.
ΔH = ‒198.4 kJ • For a pure substance (element or compound), the
standard state is usually the most stable form of the
substance at 1 atm and the temperature of interest,
which is usually 25 ⁰ C or 298 K.
When the heat of reaction, ΔHrxn, has been measured
with all the reactants and products in their standard
states, it is referred to as the standard heat of
reaction, ΔH°rxn.
FORMATION EQUATIONS
AND THEIR STANDARD ENTHALPY CHANGES
In a formation equation, 1 mole of a compound forms
from its elements.
The standard enthalpy of formation (ΔH⁰ f) of a
compound is the enthalpy change for the reaction that
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forms one mole of the compound from its elements
with all substances in their standard states. The standard state of oxygen is dioxygen (O2) not
ozone (O3).
Illustration: formation equation for methane (CH4) ΔH⁰ f of O2(g) = 0 kJ/mol
C(graphite) + 2 H2(g) → CH4(g)
ΔH⁰ f = ‒ 74.9 kJ
By definition, the standard enthalpy of formation of
Thus, the standard heat of formation of methane is the most stable form of any element is zero because
-74.9 kJ/mol. there is no formation reaction needed when the
Consider the formation of sodium chloride: element is already in its standard state.
Na(s) + 1/2Cl2 (g) → NaCl(s) Thus, the values of ΔH⁰ f for C(graphite), H2(g), O2(g),
ΔH°f = ‒ 411.1 kJ and the standard states of other elements are zero by
definition.
We usually report ΔH⁰ f values at 298 K.
If an element exists in more than one form under
2. Most compounds have a negative ΔH⁰ f.
standard conditions, the most stable form of the
Most compounds have exothermic formation reactions
element is usually used for the formation reaction.
under standard conditions which means heat is given
off when the compound forms.
Illustration:
The standard enthalpy of formation for ethanol, Selected Standard Heats of Formation at 250C
C2H5OH, is the enthalpy change for the reaction
2C(graphite) + 3H2 (g) + 1/2O2 (g) → C2H5OH(l)
ΔH°f = ‒ 277.6 kJ
The elemental source of oxygen is O2, not O or O3 ,
because O2 is the stable form of oxygen at 298 K and
atmospheric pressure.

The elemental source of carbon is graphite and not

diamond because graphite is the more stable (lower-
energy) form at 298 K and atmospheric pressure.

The most stable form of hydrogen under standard

conditions is H2(g), so this is used as the source of
hydrogen.

The stoichiometry of formation reactions always

indicates that one mole of the desired substance is
produced. As a result, standard enthalpies of
formation are reported in kJ/mol of the substance
being formed.
Two points to consider:
1. An element in its standard state is assigned a
ΔH⁰ f value of zero.
Illustration:
for Na(s), ΔH⁰ f = 0 kJ/mol
for Na(g), ΔH⁰ f = 107.8 kJ/mol
These values mean that the gaseous state is not the
most stable state of sodium at 1 atm and 298.15 K, and
that heat is required to form Na(g).

The standard state of chlorine is Cl2 molecules, not Cl

atoms
ΔH⁰ f = 0 kJ/mol for Cl2 molecules
ΔH⁰ f = 121.0 kJ/mol for Cl atoms Sample Problem 7: Writing Formation Equations
Write balanced equations for the formation of 1 mole
Several elements exist in different forms but there of each of the following compounds from their
is only one standard state. elements in their standard states and include ΔH0f.
The standard state of carbon is graphite not diamond. (a) Silver chloride, AgCl, a solid at standard conditions.
ΔH⁰ f of C(graphite) = 0 kJ/mol
 
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This handout is prepared by the faculty of the Chemistry Department, College of Science and Mathematics, MSU- Iligan Institute of Technology.  
 
(b) Calcium carbonate, CaCO3, a solid at standard
conditions.
(c) Hydrogen cyanide, HCN, a gas at standard
conditions.

Sample Problem 8: Equations Associated with

Enthalpies of Formation
For which of these reactions at 25 °C does the
enthalpy change represent a standard enthalpy of
formation? For each that does not, what changes are
needed to make it an equation whose ΔH is an enthalpy
of formation?
(a) 2 Na(s) + ½ O2 (g) ⎯→ Na2O(s)
(b) 2 K(l) + Cl2 (g) ⎯→ 2 KCl(s)
(c) C6H12O6(s) ⎯→ 6 C(diamond) + 6 H2 (g) + 3 O2 (g)

DETERMINING ΔH⁰ RXN FROM ΔH⁰ F VALUES

OF REACTANTS AND PRODUCTS

The standard heat of reaction, ΔH⁰ rxn is the sum of

the standard heats of formation of the products,
ΔH⁰ f(products) minus the sum of the standard heats of
formation of the reactants, ΔH⁰ f(reactants).

ΔH⁰ rxn = ∑m ΔH⁰ f (products) ‒ ∑n ΔH⁰ f (reactants)

Where the symbol ∑ means “sum of,” and m and n are

the amounts (mol) of the products and reactants
indicated by the coefficients from the balanced
equation.

The product of the number of moles and the enthalpy

change in kJ/mol has the units kJ:

(number of moles, mol) x (ΔH⁰ f in kJ/mol) = kJ

ΔH⁰ rxn is expressed in kJ

Sample Problem 9: Calculating the Heat of Reaction

from Heats of Formation
Nitric acid, whose worldwide annual production is
about 8 billion kilograms, is used to make many
products, including fertilizer, dyes, and explosives.
The first step in the industrial production process is
the oxidation of ammonia:
4NH3(g) + 5O2(g) ⎯⎯→ 4NO(g) + 6H2O(g)
Calculate ΔH0rxn from ΔH0f values.

 
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