17.

1: Chemical Potential Energy

1.

Gunpowder was originally developed by the Chinese in the ninth century AD, primarily for
rockets. This material is composed of charcoal, sulfur, and saltpeter (potassium nitrate). The
explosive reaction that occurs involves the conversion of the charcoal to carbon dioxide, with the
potassium nitrate providing the extra oxygen needed for a rapid reaction. Although sulfur was
included to stabilize the product, gunpowder is still highly explosive.

Types of Energy
Two basic types of energy exist: potential energy and kinetic energy. Potential energy is stored
energy. It has not yet been released, but is ready to go. Kinetic energy is the energy of motion. It
causes work to be done through movement.

Chemical Potential Energy

Energy is the capacity for doing work or supplying heat. When you fill your car with gasoline,
you are providing it with potential energy. Chemical potential energy is the energy stored in the
chemical bonds of a substance. The various chemicals that make up gasoline contain a large
amount of chemical potential energy that is released when the gasoline is burned in a controlled
way in the engine of the car. The release of that energy does two things: some of the potential
energy is transformed into work, which is used to move the car; at the same time, some of the
potential energy is converted to heat and makes the car's engine very hot. The energy changes of
a system occur as either heat or work, or some combination of both.
Figure 17.1.117.1.1: A dragster is able to accelerate because of the chemical potential energy of
its fuel. The burning of the fuel also produces large amounts of heat. (CC BY-NC; CK-12)

Dynamite is another example of chemical potential energy. The major component of dynamite is
nitroglycerin, a very unstable material. By mixing it with diatomaceous earth, the stability is
increased and it is less likely to explode if it receives a physical shock. When ignited, the
nitroglycerin explodes rapidly, releasing large amounts of nitrogen and other gases along with a
massive amount of heat.

Figure 17.1.217.1.2: Dynamite explosion. (CC BY-NC; CK-12)

Summary
• Potential energy is stored energy.
• Kinetic energy is the energy of motion.
• Chemical potential energy is energy available in the chemical bonds of a compound.
17.2: Heat
1.

Blacksmiths heat solid iron in order to shape it into a variety of different objects. Iron is a rigid,
solid metal. At room temperature, it is extremely difficult to bend iron. However, when heated to
a high enough temperature, iron can be easily worked. The heat energy in the forge is transferred
to the metal, making the iron atoms vibrate more and move around more readily.

Heat is energy that is transferred from one object or substance to another because of a difference
in temperature between the two. Heat always flows from an object at a higher temperature to an
object at a lower temperature (see figure below). The flow of heat will continue until the two
objects are at the same temperature.

Figure 17.2.117.2.1: Object A starts with a higher temperature than object B. No heat flows
when the objects are isolated from each other. When brought into contact, heat flows from A to B
until the temperatures of the two objects are the same.

Thermochemistry is the study of energy changes that occur during chemical reactions and
during changes of state. When chemical reactions occur, some chemical bonds are broken, while
new chemical bonds form. As a result of the rearrangement of atoms, the total chemical potential
energy of the system either increases or decreases.

17.3: Exothermic and Endothermic Processes

1.

A campfire is an example of basic thermochemistry. The reaction is initiated by the application

of heat from a match. The reaction converting wood to carbon dioxide and water (among other
things) continues, releasing heat energy in the process. This heat energy can then be used to cook
food, roast marshmallows, or simply to keep warm when it's cold outside.

Exothermic and Endothermic Processes

When physical or chemical changes occur, they are generally accompanied by a transfer of
energy. The law of conservation of energy states that in any physical or chemical process,
energy is neither created nor destroyed. In other words, the entire energy in the universe is
conserved. In order to better understand the energy changes taking place during a reaction, we
need to define two parts of the universe: the system and the surroundings. The system is the
specific portion of matter in a given space that is being studied during an experiment or an
observation. The surroundings is everything in the universe that is not part of the system. In
practical terms for a laboratory chemist, the system is the particular chemicals being reacted,
while the surroundings is the immediate vicinity within the room. During most processes, energy
is exchanged between the system and the surroundings. If the system loses a certain amount of
energy, that same amount of energy is gained by the surroundings. If the system gains a certain
amount of energy, that energy is supplied by the surroundings.

A chemical reaction or physical change is endothermic if heat is absorbed by the system from
the surroundings. In the course of an endothermic process, the system gains heat from the
surroundings, and so the temperature of the surroundings decreases. The quantity of heat for a
process is represented by the letter qq. The sign of qq for an endothermic process is positive
because the system is gaining heat. A chemical reaction or physical change is exothermic if heat
is released by the system into the surroundings. Because the surroundings are gaining heat from
the system, the temperature of the surroundings increases. The sign of qq for an exothermic
process is negative because the system is losing heat.

Figure 17.3.117.3.1: (A) Endothermic reaction. (B) Exothermic reaction. (CC BY-NC; CK-12)

Units of Heat
Heat flow is measured in one of two common units: the calorie and the joule. The joule (J)(J) is
the SI unit of energy. The calorie is familiar because it is commonly used when referring to the
amount of energy contained within food. A calorie (cal)(cal) is the quantity of heat required to
raise the temperature of 1 gram of water by 1oC1oC. For example, raising the temperature
of 100g100g of water from 20oC20oC to 22oC22oC would
require 100×2=200cal100×2=200cal.

Calories contained within food are actually kilocalories (kcal)(kcal). In other words, if a certain
snack contains 85 food calories, it actually contains 85kcal85kcal or 85,000cal85,000cal. In
order to make the distinction, the dietary calorie is written with a capital C.

1kilocalorie=1Calorie=1000calories(17.3.1)(17.3.1)1kilocalorie=1Calorie=1000cal
ories

To say that the snack "contains" 85 Calories means that 85kcal85kcal of energy are released
when that snack is processed by the human body.

Heat changes in chemical reactions are typically measured in joules rather than calories. The
conversion between a joule and a calorie is shown below.

1J=0.2390cal or1cal=4.184J(17.3.2)(17.3.2)1J=0.2390cal or1cal=4.184J

We can calculate the amount of heat released in kilojoules when a 400 Calorie hamburger is
digested:

400.Cal=400.kcal×4.184kJ1kcal=1.67×103kJ(17.3.3)(17.3.3)400.Cal=400.kcal×4.1
84kJ1kcal=1.67×103kJ

Summary
• The law of conservation of energy states that in any physical or chemical process, energy
is neither created nor destroyed.
• A specific portion of matter in a given space that is being studied during an experiment or
an observation is the system.
• The surroundings is everything in the universe that is not part of the system.
• A chemical reaction or physical change is endothermic if heat is absorbed by the system
from the surroundings.
• A reaction or change is exothermic if heat is released by the system into the surroundings.

17.4: Heat Capacity and Specific Heat

If a swimming pool and wading pool, both full of water at the same temperature, were subjected
to the same input of heat energy, the wading pool would certainly rise in temperature more
quickly than the swimming pool. The heat capacity of an object depends both on its mass and its
chemical composition. Because of its much larger mass, the swimming pool of water has a larger
heat capacity than the wading pool.
Heat Capacity and Specific Heat
Different substances respond to heat in different ways. If a metal chair sits in the bright sun on a
hot day, it may become quite hot to the touch. An equal mass of water under the same sun
exposure will not become nearly as hot. This means that water has a high heat capacity (the
amount of heat required to raise the temperature of an object by 1oC1oC). Water is very
resistant to changes in temperature, while metals generally are not. The specific heat of a
substance is the amount of energy required to raise the temperature of 1 gram of the substance
by 1oC1oC. The table below lists the specific heats of some common substances. The symbol
for specific heat is cpcp, with the pp subscript referring to the fact that specific heats are
measured at constant pressure. The units for specific heat can either be joules per gram per
degree (J/goC)(J/goC) or calories per gram per degree (cal/goC)(cal/goC). This text will
use J/goCJ/goC for specific heat.

Table 17.4.117.4.1: Specific Heats of Some

Substance Specific Heat (J/goC)(J/goC)

Water (l) 4.18

Water (s) 2.06

Water (g) 1.87

Ammonia (g) 2.09

Ethanol (l) 2.44

Aluminum (s) 0.897

Carbon, graphite
0.709
(s)

Copper (s) 0.385

Gold (s) 0.12

Iron (s) 0.449

Lead (s) 0.129

Mercury (l) 0.140

Silver (s) 0.233

Notice that water has a very high specific heat compared to most other substances. Water is
commonly used as a coolant for machinery because it is able to absorb large quantities of heat
(see table above). Coastal climates are much more moderate than inland climates because of the
presence of the ocean. Water in lakes or oceans absorbs heat from the air on hot days and
releases it back into the air on cool days.

Figure 17.4.117.4.1: This power plant in West Virginia, like many others, is located next to a
large lake so that the water from the lake can be used as a coolant. Cool water from the lake is
pumped into the plant, while warmer water is pumped out of the plant and back into the
lake. (CC BY-NC; CK-12)

Summary
• Heat capacity is the amount of heat required to raise the temperature of an object
by 1oC1oC.
• The specific heat of a substance is the amount of energy required to raise the temperature
of 1 gram of the substance by 1oC1Oc

17.5: Specific Heat Calculations

Water has a high capacity for absorbing heat. In a car radiator, it serves to keep the engine cooler
than it would otherwise run. As the water circulates through the engine, it absorbs heat from the
engine block. When it passes through the radiator, the cooling fan and the exposure to the outside
environment allow the water to cool somewhat before it makes another passage through the
engine.

Specific Heat Calculations

The specific heat of a substance can be used to calculate the temperature change that a given
substance will undergo when it is either heated or cooled. The equation that relates
heat (q)(q) to specific heat (cp)(cp), mass (m)(m), and temperature change (ΔT)(ΔT) is
shown below.

q=cp×m×ΔT(17.5.1)(17.5.1)q=cp×m×ΔT

The heat that is either absorbed or released is measured in joules. The mass is measured in
grams. The change in temperature is given by ΔT=Tf−TiΔT=Tf−Ti, where TfTf is the final
temperature and TiTi is the initial temperature.

Example 17.5.117.5.1
A 15.0g15.0g piece of cadmium metal absorbs 134J134J of heat while rising
from 24.0oC24.0oC to 62.7oC62.7oC. Calculate the specific heat of cadmium.

Solution

Step 1: List the known quantities and plan the problem.

Known

• Heat =q=134J=q=134J
• Mass =m=15.0g=m=15.0g
• ΔT=62.7oC−24.0oC=38.7oCΔT=62.7oC−24.0oC=38.7oC

Unknown

• cpcp of cadmium =?J/goC=?J/goC

The specific heat equation can be rearranged to solve for the specific heat.

Step 2: Solve.

cp=qm×ΔT=134J15.0g×38.7oC=0.231J/goC(17.5.2)(17.5.2)cp=qm×ΔT=134J15.0g
×38.7oC=0.231J/goC

Step 3: Think about your result.

The specific heat of cadmium, a metal, is fairly close to the specific heats of other metals. The
result has three significant figures.

Since most specific heats are known, they can be used to determine the final temperature attained
by a substance when it is either heated or cooled. Suppose that 60.0g60.0g of water
at 23.52oC23.52oC was cooled by the removal of 813J813J of heat. The change in
temperature can be calculated using the specific heat equation:

ΔT=qcp×m=813J4.18J/goC×60.0g=3.24oC(17.5.3)(17.5.3)ΔT=qcp×m=813J4.18J/g
oC×60.0g=3.24oC

Since the water was being cooled, the temperature decreases. The final temperature is:

Tf=23.52oC−3.24oC=20.28oC(17.5.4)(17.5.4)Tf=23.52oC−3.24oC=20.28oC

Summary
• The specific heat of a substance can be used to calculate the temperature change of the
substance when it is heated or cooled.
• Specific heat calculations are illustrated.

17.6: Enthalpy
1.

The factors influencing a reaction are complicated and varied. Since a catalyst affects
activation energy, we might assume it would have some sort of impact on the amount of heat that
is absorbed or released by the reaction—but it does not. The change in heat content of a reaction
depends solely on the chemical compositions of the reactants and products, not on the path taken
to get from one to the other.

Enthalpy
Heat changes in chemical reactions are often measured in the laboratory under conditions in
which the reacting system is open to the atmosphere. In these cases, the system is at a constant
pressure. Enthalpy (H)(H) is the heat content of a system at constant pressure. Chemists
routinely measure changes in enthalpy of chemical systems as reactants are converted into
products. The heat that is absorbed or released by a reaction at constant pressure is the same as
the enthalpy change, and is given the symbol ΔHΔH. Unless otherwise specified, all reactions in
this material are assumed to take place at constant pressure.

The change in enthalpy of a reaction is a measure of the differences in enthalpy of the reactants
and products. The enthalpy of a system is determined by the energies needed to break chemical
bonds and the energies needed to form chemical bonds. Energy needs to be put into the system in
order to break chemical bonds—they do not come apart spontaneously in most cases. Bond
formation to produce products will involve release of energy. The change in enthalpy shows the
trade-offs made in these two processes. Does it take more energy to break bonds than that needed
to form bonds? If so, the reaction is endothermic and the enthalpy change is positive. If more
energy is produced in bond formation than that needed for bond breaking, the reaction is
exothermic and the enthalpy is negative.

Several factors influence the enthalpy of a system. Enthalpy is an extensive property, determined
in part by the amount of material being dealt with. The state of reactants and products (solid,
liquid, or gas) influences the enthalpy value for a system. The direction of the reaction affects the
enthalpy value. A reaction that takes place in the opposite direction has the same numerical
enthalpy value, but the opposite sign.

Summary
• Enthalpy, the heat content of a system at constant pressure, is related to the heat of
reaction.
• The enthalpy of a system is determined by the energies needed to break chemical bonds
and the energies needed to form chemical bonds.
• Factors that influencing enthalpy include: amount of materials, the state of reactants and
products, and direction of the reaction.

17.7: Calorimetry
1.

At one time, calories in foods were measured with a bomb calorimeter. A weighed amount of the
food would be placed in the calorimeter and the system was then sealed and filled with oxygen.
An electric spark ignited the food-oxygen mixture. The amount of heat released when the food
burned gave an idea of the calories present within the food. Today, calories are calculated from
the protein, carbohydrate, and fat content of food (all determined by chemical analysis).

Calorimetry
Calorimetry is the measurement of the transfer of heat into or out of a system during a chemical
reaction or physical process. A calorimeter is an insulated container that is used to measure heat
changes. The majority of reactions that can be analyzed in a calorimetry experiment are either
liquids or aqueous solutions. A frequently used and inexpensive calorimeter is a set of nested
foam cups fitted with a lid to limit the heat exchange between the liquid in the cup and the air in
the surroundings (see figure below). In a typical calorimetry experiment, specific volumes of the
reactants are dispensed into separate containers and the temperature of each is measured. They
are then mixed into the calorimeter, which starts the reaction. The reactant mixture is stirred until
the reaction is complete, while the temperature of the reaction is continuously monitored.
 Figure 17.7.117.7.1: A simple constant-pressure calorimeter. (CC BY-
NC; CK-12)

The key to all calorimetry experiments is the assumption that there is no heat exchange between
the insulated calorimeter and the room. Consider the case of a reaction taking place between
aqueous reactants: the water in which the solids have been dissolved is the surroundings, while
the dissolved substances are the system. The temperature change that is measured is the
temperature change that is occurring in the surroundings. If the temperature of the water
increases as the reaction occurs, the reaction is exothermic. Heat was released by the system into
the surrounding water. An endothermic reaction absorbs heat from the surroundings, so the
temperature of the water decreases as heat leaves the surroundings to enter the system.

The temperature change of the water is measured in the experiment and the specific heat of water
can be used to calculate the heat absorbed by the surroundings (qsurr)(qsurr).

qsurr=m×cp×ΔT(17.7.1)(17.7.1)qsurr=m×cp×ΔT

In the equation, mm is the mass of the water, cpcp is the specific heat of the water,
and ΔTΔT is Tf−TiTf−Ti. The heat absorbed by the surroundings is equal, but opposite in sign,
to the heat released by the system. Because the heat change is determined at constant pressure,
the heat released by the system (qsys)(qsys) is equal to the enthalpy change (ΔH)(ΔH).

qsys=ΔH=−qsurr=−(m×cp×ΔT)(17.7.2)(17.7.2)qsys=ΔH=−qsurr=−(m×cp×ΔT)

The sign of ΔHΔH is positive for an endothermic reaction and negative for an exothermic
reaction.

Example 17.7.117.7.1
In an experiment, 25.0mL25.0mL of 1.00MHCl1.00MHCl at 25.0oC25.0oC is added
to 25.0mL25.0mL of 1.00MNaOH1.00MNaOH at 25.0oC25.0oC in a foam cup
calorimeter. A reaction occurs and the temperature rises to 32.0oC32.0oC. Calculate the
enthalpy change (ΔH)(ΔH) in kJkJ for this reaction. Assume the densities of the solutions
are 1.00g/mL1.00g/mL and that their specific heat is the same as that of water.
Solution

Step 1: List the known quantities and plan the problem.

Known

• cp=4.18J/goCcp=4.18J/goC
• Vfinal=25.0mL+25.0mL=50.0mLVfinal=25.0mL+25.0mL=50.0mL
• ΔT=32.0oC−25.0oC=7.0oCΔT=32.0oC−25.0oC=7.0oC
• Density =1.00g/mL=1.00g/mL

Unknown

• ΔH=?kJΔH=?kJ

The volume and density can be used to find the mass of the solution after mixing. Then calculate
the change in enthalpy by
using ΔH=qsys=−qsurr=−(m×cp×ΔT)ΔH=qsys=−qsurr=−(m×cp×ΔT).

Step 2: Solve.

mΔH=50.0mL×1.00gmL=50.0g=−(m×cp×ΔT)=−(50.0g×4.18J/goC×7.0oC)=−146
3J=−1.5kJ(17.7.3)(17.7.4)(17.7.3)m=50.0mL×1.00gmL=50.0g(17.7.4)ΔH=−(m×cp×Δ
T)=−(50.0g×4.18J/goC×7.0oC)=−1463J=−1.5kJ

Step 3: Think about the result.

The enthalpy change is negative because the reaction releases heat to the surroundings, resulting
in an increase in the temperature of the water.

Summary
• Calorimetry is the measurement of the transfer of heat into or out of a system during a
chemical reaction or physical process.
• A calorimeter is an insulated container that is used to measure heat changes.
• Calculations involving enthalpy changes are illustrated.

17.8: Thermochemical Equations

1.

Heating a home is becoming more and more expensive. The decision to use gas, oil, electricity,
or wood can be multi-faceted. Part of the decision is based on which fuel will provide the highest
amount of energy release when burned. Studies of thermochemistry can be very useful in getting
reliable information for making these important choices.

Thermochemical Equation
When methane gas is combusted, heat is released, making the reaction exothermic. Specifically,
the combustion of 1mol1mol of methane releases 890.4 kilojoules of heat energy. This
information can be shown as part of a balanced equation:

CH4(g)+2O2(g)→CO2(g)+2H2O(l)+890.4kJ(17.8.1)(17.8.1)CH4(g)+2O2(g)→CO2(
g)+2H2O(l)+890.4kJ

The equation tells us that 1mol1mol of methane combines with 2mol2mol of oxygen to
produce 1mol1mol of carbon dioxide and 2mol2mol of water. In the
process, 890.4kJ890.4kJ is released and so it is written as a product of the reaction.
A thermochemical equation is a chemical equation that includes the enthalpy change of the
reaction. The process in the above thermochemical equation can be shown visually in the figure
below.

Figure 17.8.117.8.1: (A) As reactants are converted to products in an exothermic reaction,

enthalpy is released into the surroundings. The enthalpy change of the reaction is negative. (B)
As reactants are converted to products in an endothermic reaction, enthalpy is absorbed from
the surroundings. The enthalpy change of the reaction is positive. (CC BY-NC; CK-12)

In the combustion of methane example, the enthalpy change is negative because heat is being
released by the system. Therefore, the overall enthalpy of the system decreases. The heat of
reaction is the enthalpy change for a chemical reaction. In the case above, the heat of reaction
is −890.4kJ−890.4kJ. The thermochemical reaction can also be written in this way:

CH4(g)+2O2(g)→CO2(g)+2H2O(l)ΔH=−890.4kJ(17.8.2)(17.8.2)CH4(g)+2O2(g)→
CO2(g)+2H2O(l)ΔH=−890.4kJ
Heats of reaction are typically measured in kilojoules. It is important to include the physical
states of the reactants and products in a thermochemical equation, as the value of
the ΔHΔH depends on those states.

Endothermic reactions absorb energy from the surroundings as the reaction occurs.
When 1mol1mol of calcium carbonate decomposes into 1mol1mol of calcium oxide
and 1mol1mol of carbon dioxide, 177.8kJ177.8kJ of heat is absorbed. The process is shown
visually in the figure above (B). The thermochemical reaction is shown below.

CaCO3(s)+177.8kJ→CaO(s)+CO2(g)(17.8.3)(17.8.3)CaCO3(s)+177.8kJ→CaO(s)+C
O2(g)

Because the heat is absorbed by the system, the 177.8kJ177.8kJ is written as a reactant. The
heat of reaction is positive for an endothermic reaction.

CaCO3(s)→CaO(s)+CO2(g)ΔH=177.8kJ(17.8.4)(17.8.4)CaCO3(s)→CaO(s)+CO2(g)
ΔH=177.8kJ

The way in which a reaction is written influences the value of the enthalpy change for the
reaction. Many reactions are reversible, meaning that the product(s) of the reaction are capable of
combining and reforming the reactant(s). If a reaction is written in the reverse direction, the sign
of the ΔHΔH changes. For example, we can write an equation for the reaction of calcium oxide
with carbon dioxide to form calcium carbonate:

CaO(s)+CO2(g)→CaCO3(s)+177.8kJ(17.8.5)(17.8.5)CaO(s)+CO2(g)→CaCO3(s)+17
7.8kJ

The reaction is exothermic and thus the sign of the enthalpy change is negative.

CaO(s)+CO2(g)→CaCO3(s)ΔH=−177.8kJ(17.8.6)(17.8.6)CaO(s)+CO2(g)→CaCO3(s
)ΔH=−177.8kJ

Summary
• A thermochemical equation is a chemical equation that includes the enthalpy change of
the reaction.
• The heat of reaction is the enthalpy change for a chemical reaction.
17.9: Stoichiometric Calculations and
Enthalpy Changes
1.

There is a growing concern about damage to the environment done by emissions from
manufacturing plants. Many companies are taking steps to reduce these harmful emissions by
adding equipment that will trap the pollutants. In order to know what equipment (and the
quantity) to order, studies are done to measure the amount of product currently produced. Since
pollution is often both particulate and thermal, energy changes need to be determined in addition
to the amounts of products released.

Stoichiometric Calculations and Enthalpy Changes

Chemistry problems that involve enthalpy changes can be solved by techniques similar to
stoichiometry problems. Refer again to the combustion reaction of methane. Since the reaction
of 1mol1mol of methane released 890.4kJ890.4kJ, the reaction of 2mol2mol of methane
would release 2×890.4kJ=1781kJ2×890.4kJ=1781kJ. The reaction of 0.5mol0.5mol of
methane would release 890,4kJ2=445.2kJ890,4kJ2=445.2kJ. As with other stoichiometry
problems, the moles of a reactant or product can be linked to mass or volume.

Example 17.9.117.9.1
Sulfur dioxide gas reacts with oxygen to form sulfur trioxide in an exothermic reaction,
according to the following thermochemical equation.

2SO2(g)+O2(g)→2SO3(g)+198kJ(17.9.1)(17.9.1)2SO2(g)+O2(g)→2SO3(g)+198kJ

Calculate the enthalpy change that occurs when 58.0g58.0g of sulfur dioxide is reacted with
excess oxygen.

Solution:

Step 1: List the known quantities and plan the problem.

• Mass SO2=58.0gSO2=58.0g
• Molar mass SO2=64.07g/molSO2=64.07g/mol
• ΔH=−198kJΔH=−198kJ for the reaction of 2molSO22molSO2

Unknown

• ΔH=?kJΔH=?kJ
The calculation requires two steps. The mass of SO2SO2 is converted to moles. Then the moles
of SO2SO2 is multiplied by the conversion factor of (−198kJ2molSO2)(−198kJ2molSO2).

Step 2: Solve.

ΔH=58.0gSO2×1molSO264.07gSO2×−198kJ2molSO2=89.6kJ(17.9.2)(17.9.2)ΔH=
58.0gSO2×1molSO264.07gSO2×−198kJ2molSO2=89.6kJ

Step 3: Think about your result.

The mass of sulfur dioxide is slightly less than 1mol1mol. Since 198kJ198kJ is released for
every 2mol2mol of SO2SO2 that reacts, the heat released when about 1mol1mol reacts is one
half of 198. The 89.6kJ89.6kJ is slightly less than half of 198. The sign of ΔHΔH is negative
because the reaction is exothermic.

Summary
• Chemistry problems that involve enthalpy changes can be solved by techniques similar to
stoichiometry problems.
• Calculations of energy changes in enthalpy equations are described.
17.10: Heats of Fusion and Solidification
1.

Suppose that you are holding an ice cube in your hand. It feels cold because heat energy leaves
your hand and enters the ice cube. What happens to the ice cube? It melts. However, the
temperature during a phase change remains constant. So the heat that is being lost by your hand
does not raise the temperature of the ice above its melting temperature of 0oC0oC. Rather, all
the heat goes into the change of state. Energy is absorbed during the process of changing ice into
water. The water that is produced also remains at 0oC0oC until all of the ice is melted.

Heats of Fusion and Solidification

All solids absorb heat as they melt to become liquids. The gain of heat in this endothermic
process goes into changing the state, rather than changing the temperature. The molar heat of
fusion (ΔHfus)(ΔHfus) of a substance is the heat absorbed by one mole of that substance as it is
converted from a solid to a liquid. Since the melting of any substance absorbs heat, it follows
that the freezing of any substance releases heat. The molar heat of
solidification (ΔHsolid)(ΔHsolid) of a substance is the heat released by one mole of that
substance as it is converted from a liquid to a solid. Since fusion and solidification of a given
substance are the exact opposite processes, the numerical value of the molar heat of fusion is the
same as the numerical value of the molar heat of solidification, but opposite in sign. In other
words, ΔHfus=−ΔHsolidΔHfus=−ΔHsolid. The figure below shows all of the possible changes
of state along with the direction of heat flow during each process.
Figure 17.10.117.10.1: From left to right, heat is absorbed from the surroundings during
melting, evaporation, and sublimation. From right to left, heat is released to the surroundings
during freezing, condensation, and deposition. (CC BY-NC; CK-12)

Every substance has a unique value for its molar heat of fusion, depending on the amount of
energy required to disrupt the intermolecular forces present in the solid. When 1mol1mol of ice
at 0oC0oC is converted to 1mol1mol of liquid water at 0oC0oC, 6.01kJ6.01kJ of heat are
absorbed from the surroundings. When 1mol1mol of water at 0oC0oC freezes to ice
at 0oC0oC, 6.01kJ6.01kJ of heat is released into the surroundings.

H2O(s)→H2O(l)H2O(l)→H2O(s)ΔHfus=6.01kJ/molΔHsolid=−6.01kJ/mol(17.10.1)
(17.10.1)H2O(s)→H2O(l)ΔHfus=6.01kJ/molH2O(l)→H2O(s)ΔHsolid=−6.01kJ/mol

The molar heats of fusion and solidification of a given substance can be used to calculate the
heat absorbed or released when various amounts are melted or frozen.

Example 17.10.117.10.1
Calculate the heat absorbed when 31.6g31.6g of ice at 0oC0oC is completely melted.

Solution

Step 1: List the known quantities and plan the problem.

Known

• Mass =31.6g=31.6g ice

• Molar mass H2O=18.02g/molH2O=18.02g/mol
• Molar heat of fusion =6.01kJ/mol=6.01kJ/mol

Unknown

• ΔH=?JΔH=?J

The mass of ice is first converted to moles. This is then multiplied by the conversion factor
of (6.01kJ1mol)(6.01kJ1mol) in order to find the kJkJ of heat absorbed.

Step 2: Solve.

31.6g ice×1mol ice18.02g ice×6.01kJ1mol ice=10.5kJ(17.10.2)(17.10.2)31.6g

ice×1mol ice18.02g ice×6.01kJ1mol ice=10.5kJ

Step 3: Think about your result.

The given quantity is a bit less than 2 moles of ice, and so just less than 12kJ12kJ of heat is
absorbed by the melting process.

Summary
• The molar heat of fusion (ΔHfus)(ΔHfus) of a substance is the heat absorbed by one
mole of that substance as it is converted from a solid to a liquid.
• The molar heat of solidification (ΔHsolid)(ΔHsolid) of a substance is the heat released
by one mole of that substance as it is converted from a liquid to a solid.
• Calculations of heat changes during fusion and solidification are described.

17.11: Heats of Vaporization and

Condensation
1.

Natural resources for electric power generation have traditionally been waterfalls, oil, coal, or
nuclear power. Research is being carried out to look for other renewable sources to run the
generators. Geothermal sites (such as geysers) are being considered because of the steam they
produce. Capabilities can be estimated by knowing how much steam is released in a given time
at a particular site.
Heat of Vaporization and Condensation
Energy is absorbed in the process of converting a liquid at its boiling point into a gas. As with
the melting point of a solid, the temperature of a boiling liquid remains constant and the input of
energy goes into changing the state. The molar heat of vaporization (ΔHvap)(ΔHvap) of a
substance is the heat absorbed by one mole of that substance as it is converted from a liquid to a
gas. As a gas condenses to a liquid, heat is released. The molar heat of
condensation (ΔHcond)(ΔHcond) of a substance is the heat released by one mole of that
substance as it is converted from a gas to a liquid. Since vaporization and condensation of a
given substance are the exact opposite processes, the numerical value of the molar heat of
vaporization is the same as the numerical value of the molar heat of condensation, but opposite
in sign. In other words, ΔHvap=−ΔHcondΔHvap=−ΔHcond.

When 1mol1mol of water at 100oC100oC and 1atm1atm pressure is converted

to 1mol1mol of water vapor at 100oC100oC, 40.7kJ40.7kJ of heat is absorbed from the
surroundings. When 1mol1mol of water vapor at 100oC100oC condenses to liquid water
at 100oC100oC, 40.7kJ40.7kJ of heat is released into the surroundings.

H2O(l)→H2O(g)H2O(g)→H2O(l)ΔHvap=40.7kJ/molΔHcond=−40.7kJ/mol(17.11.1
)(17.11.1)H2O(l)→H2O(g)ΔHvap=40.7kJ/molH2O(g)→H2O(l)ΔHcond=−40.7kJ/mol

Other substances have different values for their molar heats of fusion and vaporization; these
substances are summarized in the table below.

Table 17.11.117.11.1: Molar Heats of Fusi

Substance ΔHfusΔHfus (kJ/mol)(kJ/mol)

Ammonia (NH3)(NH3) 5.65

Ethanol (C2H5OH)(C2H5OH) 4.60

Methanol (CH3OH)(CH3OH) 3.16

Oxygen (O2)(O2) 0.44

Water (H2O)(H2O) 6.01

Notice that for all substances, the heat of vaporization is substantially higher than the heat of
fusion. Much more energy is required to change the state from a liquid to a gas than from a solid
to a liquid. This is because of the large separation of the particles in the gas state. The values of
the heats of fusion and vaporization are related to the strength of the intermolecular forces. All of
the substances in the table above, with the exception of oxygen, are capable of hydrogen
bonding. Consequently, the heats of fusion and vaporization of oxygen are far lower than the
others.

Example 17.11.117.11.1
What mass of methanol vapor condenses to a liquid as 20.0kJ20.0kJ of heat is released?

Solution

Step 1: List the known quantities and plan the problem.

Known

• ΔH=20.0kJΔH=20.0kJ
• ΔHcond=−35.3kJ/molΔHcond=−35.3kJ/mol
• Molar mass CH3OH=32.05g/molCH3OH=32.05g/mol

Unknown

• Mass methanol =?g=?g

First the kJkJ of heat released in the condensation is multiplied by the conversion
factor (1mol−35.3kJ)(1mol−35.3kJ) to find the moles of methanol that condensed. Then, moles
are converted to grams.

Step 2: Solve.

−20.0kJ×1molCH3OH−35.3kJ×32.05gCH3OH1molCH3OH=18.2gCH3OH(17.11.2
)(17.11.2)−20.0kJ×1molCH3OH−35.3kJ×32.05gCH3OH1molCH3OH=18.2gCH3OH

Step 3: Think about your result.

Condensation is an exothermic process, so the enthalpy change is negative. Slightly more than
one-half mole of methanol is condensed.

Summary
• The molar heat of vaporization (ΔHvap)(ΔHvap) is the heat absorbed by one mole of
a substance as it is converted from a liquid to a gas.
• The molar heat of condensation (ΔHcond)(ΔHcond) is the heat released by one mole of
a substance as it is converted from a gas to a liquid.
• Examples of calculations involving the molar heat of vaporization and condensation are
illustrated.
17.12: Multi-Step Problems with Changes of
State
1.

If you have a cube of ice, which process will take more energy—the melting of that ice cube or
the conversion of the water to steam? The short answer is that more energy is needed to convert
the water to steam. The long answer is really a series of questions: How do you get from one
point to the other? What is the temperature of the ice? What is the mass of that ice cube? A long
process is involved to take the material from the starting point to the end point.

Multi-Step Problems with Changes of State

Heating curves show the phase changes that a substance undergoes as heat is continuously
absorbed.

Figure 17.12.117.12.1: Heating curve of water. (CC BY-NC; CK-12)

The specific heat of a substance allows us to calculate the heat absorbed or released as the
temperature of the substance changes. It is possible to combine that type of problem with a
change of state to solve a problem involving multiple steps. The figure above shows ice
at −30oC−30oC being converted in a five-step process to gaseous water (steam)
at 140oC140oC. It is now possible to calculate the heat absorbed during that entire process. The
process and the required calculations are summarized below.
 1. Ice is heated from −30oC−30oC to 0oC0oC. The heat absorbed is calculated by using
the specific heat of ice and the equation ΔH=cp×m×ΔTΔH=cp×m×ΔT.

2. Ice is melted at 0oC0oC. The heat absorbed is calculated by multiplying the moles of ice
by the molar heat of fusion.

3. Water at 0oC0oC is heated to 100oC100oC. The heat absorbed is calculated by using

the specific heat of water and the equation ΔH=cp×m×ΔTΔH=cp×m×ΔT.

4. Water is vaporized to steam at 100oC100oC. The heat absorbed is calculated by

multiplying the moles of water by the molar heat of vaporization.

5. Steam is heated from 100oC100oC to 140oC140oC. The heat absorbed is calculated

by using the specific heat of steam and the equation ΔH=cp×m×ΔTΔH=cp×m×ΔT.

Example 17.12.117.12.1
Calculate the total amount of heat absorbed (in kJkJ) when 2.00mol2.00mol of ice
at −30oC−30oC is converted to steam at 140.0oC140.0oC. The required specific heats can be
found in the table in "Heat Capacity and Specific Heat".

Solution

Step 1: List the known quantities and plan the problem.

Known

• 2.00mol2.00mol ice =36.04g=36.04g ice

• cpcp (ice) =2.06J/goC=2.06J/goC
• cpcp (water) =4.18J/goC=4.18J/goC
• cpcp (steam) =1.87J/goC=1.87J/goC
• ΔHfus=6.01kJ/molΔHfus=6.01kJ/mol
• ΔHvap=40.7kJ/molΔHvap=40.7kJ/mol

Unknown

• ΔHtotal=?kJΔHtotal=?kJ

Follow the steps previously described. Note that the mass of the water is needed for the
calculations that involve the specific heat, while the moles of water is needed for the calculations
that involve changes of state. All heat quantities must be in kilojoules so that they can be added
together to get a total for the five-step process.
Step 2: Solve.

1. ΔH1=2.06J/goC×36.04g×30oC×1kJ1000J=2.23kJ(17.12.1)(17.12.1)Δ
H1=2.06J/goC×36.04g×30oC×1kJ1000J=2.23kJ
2. ΔH2=2.00mol×6.01kJ1mol=12.0kJ(17.12.2)(17.12.2)ΔH2=2.00mol×6
.01kJ1mol=12.0kJ
3. ΔH3=4.18J/goC×36.04g×100oC×1kJ1000kJ=15.1kJ(17.12.3)(17.12.3
)ΔH3=4.18J/goC×36.04g×100oC×1kJ1000kJ=15.1kJ
4. ΔH4=2.00mol×40.7kJ1mol=81.4kJ(17.12.4)(17.12.4)ΔH4=2.00mol×4
0.7kJ1mol=81.4kJ
5. ΔH5=1.87J/goC×36.04g×40oC×1kJ1000J=2.70kJ(17.12.5)(17.12.5)Δ
H5=1.87J/goC×36.04g×40oC×1kJ1000J=2.70kJ
ΔHtotal=ΔH1+ΔH2+ΔH3+ΔH4+ΔH5=113.4kJ(17.12.6)(17.12.6)ΔHtotal=ΔH1+ΔH2+
ΔH3+ΔH4+ΔH5=113.4kJ

Step 3: Think about your result.

The total heat absorbed as the ice at −30oC−30oC is heated to steam

at 140oC140oC is 133.4kJ133.4kJ. The largest absorption of heat comes during the
vaporization of the liquid water.

Summary
• Multi-step calculations for changes of state are described.
17.13: Heat of Solution
1.

When preparing dilutions of concentrated sulfuric acid, the directions usually call for adding the
acid slowly to water with frequent stirring. When this acid is mixed with water, a great deal of
heat is released in the dissolution process. If water were added to acid, the water would quickly
heat and splatter, causing harm to the person making the solution.

Heat of Solution
Enthalpy changes also occur when a solute undergoes the physical process of dissolving into a
solvent. Hot packs and cold packs (see figure below) use this property. Many hot packs use
calcium chloride, which releases heat when it dissolves, according to the equation below.

CaCl2(s)→Ca2+(aq)+2Cl−(aq)+82.8kJ(17.13.1)(17.13.1)CaCl2(s)→Ca2+(aq)+2Cl−(
aq)+82.8kJ

The molar heat of solution (ΔHsoln)(ΔHsoln) of a substance is the heat absorbed or released
when one mole of the substance is dissolved in water. For calcium
chloride, ΔHsoln=−82.8kJ/molΔHsoln=−82.8kJ/mol.

Figure 17.13.117.13.1: Chemical hot packs and cold packs work because of the heats of
solution of the chemicals inside them. When the bag is squeezed, an inner pouch bursts, allowing
the chemical to dissolve in water. Heat is released in the hot pack and absorbed in the cold pack.
(CC BY-NC; CK-12)

Many cold packs use ammonium nitrate, which absorbs heat from the surroundings when it
dissolves.
NH4NO3(s)+25.7kJ→NH+4(aq)+NO−3(aq)(17.13.2)(17.13.2)NH4NO3(s)+25.7kJ→
NH4+(aq)+NO3−(aq)

Cold packs are typically used to treat muscle strains and sore joints. The cold pack is activated
and applied to the affected area. As the ammonium nitrate dissolves, it absorbs heat from the
body and helps to limit swelling. For ammonium
nitrate, ΔHsoln=25.7kJ/molΔHsoln=25.7kJ/mol.

Example 17.13.117.13.1
The molar heat of solution, ΔHsolnΔHsoln,
of NaOHNaOH is −44.51kJ/mol−44.51kJ/mol. In a certain
experiment, 50.0g50.0g of NaOHNaOH is completely dissolved
in 1.000L1.000L of 20.0oC20.0oC water in a foam cup calorimeter. Assuming no heat loss,
calculate the final temperature of the water.

Solution

Step 1: List the known quantities and plan the problem.

Known

• Mass NaOH=50.0gNaOH=50.0g
• Molar mass NaOH=40.00g/molNaOH=40.00g/mol
• ΔHsoln(NaOH)=−44.51kJ/molΔHsoln(NaOH)=−44.51kJ/mol
• Mass H2O=1.000kg=1000.gH2O=1.000kg=1000.g (assumes
density =1.00g/mL=1.00g/mL)
• Tinitial(H2O)=20.0oCTinitial(H2O)=20.0oC
• cp(H2O)=4.18J/goCcp(H2O)=4.18J/goC

Unknown

• TfinalTfinal of H2O=?oCH2O=?oC

This is a multiple-step problem:

1) Grams NaOHNaOH is converted to moles.

2) Moles is multiplied by the molar heat of solution.

3) The joules of heat released in the dissolution process is used with the specific heat equation
and the total mass of the solution to calculate the ΔTΔT.
4) The TfinalTfinal is determined from ΔTΔT.

Step 2: Solve.

50.0gNaOH×1molNaOH40.00gNaOH×−44.51kJ1molNaOH×1000J1kJ=−5.56×1
04J(17.13.3)(17.13.3)50.0gNaOH×1molNaOH40.00gNaOH×−44.51kJ1molNaOH×100
0J1kJ=−5.56×104J
ΔT=ΔHcp×m=−5.56×104J4.18J/goC×1050g=13.2oC(17.13.4)(17.13.4)ΔT=ΔHcp×
m=−5.56×104J4.18J/goC×1050g=13.2oC
Tfinal=20.0oC+13.2oC=33.2oC(17.13.5)(17.13.5)Tfinal=20.0oC+13.2oC=33.2oC

Step 3: Think about your result.

The dissolution process releases a large amount of heat, which causes the temperature of the
solution to rise. Care must be taken when preparing concentrated solutions of sodium hydroxide,
because of the large amounts of heat released.

Summary
• The molar heat of solution (ΔHsoln)(ΔHsoln) of a substance is the heat absorbed or
released when one mole of the substance is dissolved in water.
• Sample calculations using molar heat of solution are given.
17.14: Heat of Combustion
1.

In efforts to reduce gas consumption from oil, ethanol is often added to regular gasoline. It has a
high octane rating and burns more slowly than regular gas. This "gasohol" is widely used in
many countries. It produces somewhat lower carbon monoxide and carbon dioxide emissions,
but does increase air pollution from other materials.

Molar Heat of Combustion

Many chemical reactions are combustion reactions. It is often important to know the energy
produced in such a reaction so that we can determine which fuel might be the most efficient for a
given purpose. The molar heat of combustion (He)(He) is the heat released when one mole of
a substance is completely burned.

Typical combustion reactions involve the reaction of a carbon-containing material with oxygen
to form carbon dioxide and water as products. If methanol is burned in air, we have:

CH3OH+O2→CO2+2H2OHe=890kJ/mol(17.14.1)(17.14.1)CH3OH+O2→CO2+2H2
OHe=890kJ/mol

In this case, one mole of oxygen reacts with one mole of methanol to form one mole of carbon
dioxide and two moles of water.

It should be noted that inorganic substances can also undergo a form of combustion reaction:

2Mg+O2→2MgO(17.14.2)(17.14.2)2Mg+O2→2MgO

In this case, there is no water and no carbon dioxide formed. For the purposes of this chapter,
these reactions are generally not considered in the discussion of combustion reactions.

Example 17.14.117.14.1
Heats of combustion are usually determined by burning a known amount of the material in a
bomb calorimeter with an excess of oxygen. By measuring the temperature change, the heat of
combustion can be determined.

A 1.55 gram sample of ethanol is burned and produced a temperature increase of 55oC55oC in
200 grams of water. Calculate the molar heat of combustion.

Solution

Step 1: List the known quantities and plan the problem.

Known

• Mass of ethanol =1.55g=1.55g

• Molar mass of ethanol =46.1g/mol=46.1g/mol
• Mass of water =200g=200g
• cpcp water =4.18J/goC=4.18J/goC
• Temperature increase =55oC=55oC

Unknown

• HeHe of ethanol

Step 2: Solve.

Amount of ethanol used:

1.55g46.1g/mol=0.0336mol(17.14.3)(17.14.3)1.55g46.1g/mol=0.0336mol

Energy generated:

4.184J/goC×200g×55oC=46024J=46.024kJ(17.14.4)(17.14.4)4.184J/goC×200g×55
oC=46024J=46.024kJ

Molar heat of combustion:

46.024kJ0.0336mol=1370kJ/mol(17.14.5)(17.14.5)46.024kJ0.0336mol=1370kJ/m
ol

Step 3: Think about your result.

The burning of ethanol produces a significant amount of heat.

Summary
• The molar heat of combustion (He)(He) is the heat released when one mole of a
substance is completely burned.
• Calculations using the molar heat of combustion are described.
17.15: Hess's Law of Heat Summation
1.

Calculating the energy involved in the operation of an acetylene torch is no simple matter. Since
there is a complex series of reactions taking place, simple methods for determining the heat of
reaction will not work. We need to develop new approaches to these calculations.

Adding Heats of Reaction

It is sometimes very difficult or even impossible to measure the enthalpy change for a reaction
directly in the laboratory. Some reactions take place extremely slowly, making a direct
measurement unfeasible. In other cases, a given reaction may be an intermediate step in a series
of reactions. Some reactions may be difficult to isolate because multiple side reactions may
occur at the same time. Fortunately, it is possible to measure the enthalpy change for a reaction
with an indirect method. Hess's law of heat summation states that if two or more
thermochemical equations can be added together to give a final equation, then the heats of
reaction can also be added to give a heat of reaction for the final equation.

An example will illustrate how Hess's law can be used. Acetylene (C2H2)(C2H2) is a gas that
burns at an extremely high temperature (3300oC)(3300oC) and is used in welding. On paper,
acetylene gas can be produced by the reaction of solid carbon (graphite) with hydrogen gas.

2C(s,graphite)+H2(g)→C2H2(g)ΔH=?(17.15.1)

Unfortunately, this reaction would be virtually impossible to perform in the laboratory because
carbon would react with hydrogen to form many different hydrocarbon products simultaneously.
There is no way to create conditions under which only acetylene would be produced.

However, enthalpy changes for combustion reactions are relatively easy to measure. The heats of
combustion for carbon, hydrogen, and acetylene are shown below, along with each balanced
equation.

C(s,graphite)+O2(g)→CO2(g) ΔH=−393.5kJ

H2(g)+12O2(g)→H2O(l) ΔH=−285.8kJ (17.15.2)

C2H2(g)+52O2(g)→2CO2(g)+H2O(l) ΔH=−1301.1kJ

To use Hess's law, we need to determine how the three equations above can be manipulated so
that they can be added together to result in the desired equation (the formation of acetylene from
carbon and hydrogen).
In order to do this, we will go through the desired equation, one substance at a time—choosing
the combustion reaction from the equations above that contains that substance. It may be
necessary to either reverse a combustion reaction, or multiply it by some factor in order to make
it "fit" to the desired equation. The first reactant is carbon and in the equation for the desired
reaction, the coefficient of the carbon is a 2. So, we will write the first combustion reaction,
doubling all of the coefficients and the ΔHΔH:

2C(s,graphite)+2O2(g)→2CO2(g)ΔH=2(−393.5)=−787.0kJ(17.15.3

The second reactant is hydrogen and its coefficient is a 1, as it is in the second combustion
reaction. Therefore, that reaction will be used as written.

H2(g)+12O2(g)→H2O(l)ΔH=−285.8kJ(17.15.4)

The product of the reaction is C2H2C2H2 and its coefficient is also a 1. In combustion reaction
#3, the acetylene is a reactant. Therefore, we will reverse reaction 3, changing the sign of
the ΔHΔH:

2CO2(g)+H2O(l)→C2H2(g)+52O2(g)ΔH=1301.1kJ(17.15.5)

Now, these three reactions can be summed together. Any substance that appears in equal
quantities as a reactant in one equation and a product in another equation cancels out
algebraically. The values for the enthalpy changes are likewise added.

So, the heat of reaction for the combination of carbon with hydrogen to produce acetylene
is 228.3kJ228.3kJ. When one mole of acetylene is produced, 228.3kJ228.3kJ of heat is
absorbed, making the reaction endothermic.

Summary
• Hess's law of heat summation states that if two or more thermochemical equations can be
added together to give a final equation, then the heats of reaction can also be added to
give a heat of reaction for the final equation.
 • Hess's law is used to calculate the heat of reaction for processes that cannot be measured
directly.

17.16: Standard Heat of Formation

1.

Table 17.16.117.16.1: Standard Heats of Formation of Select

Substance ΔHofΔHfo (kJ/mol)(kJ/mol) Substance

Al2O3(s)Al2O3(s) -1669 H2O2(l)H2O2(l)

BaCl2(s)BaCl2(s) -860.1 KCl(s)KCl(s)
Br2(g)Br2(g) 30.91 NH3(g)NH3(g)
C(s,graphite)C(s,graphite) 0 NO(g)NO(g)
C(s,diamond)C(s,diamond) 1.90 NO2(g)NO2(g)
CH4(g)CH4(g) -74.85 NaCl(s)NaCl(s)
C2H5OH(l)C2H5OH(l) -276.98 O3(g)O3(g)
CO(g)CO(g) -110.5 P(s,white)P(s,white)
CO2(g)CO2(g) -393.5 P(s,red)P(s,red)
CaO(s)CaO(s) -635.6 PbO(s)PbO(s)
CaCO3(s)CaCO3(s) -1206.9 S(rhombic)S(rhombic)
HCl(g)HCl(g) -92.3 S(monoclinic)S(monocli
CuO(s)CuO(s) -155.2 SO2(g)SO2(g)
CuSO4(s)CuSO4(s) -769.86 SO3(g)SO3(g)
Fe2O3(s)Fe2O3(s) -822.2 H2S(s)H2S(s)
H2O(g)H2O(g) -241.8 SiO2(s)SiO2(s)
H2O(l)H2O(l) -285.8 ZnCl2(s)ZnCl2(s)
The Hope diamond, a form of carbon, is a very expensive piece of jewelry—currently worth
about $350,000,000. A graphite pencil, comprised partly of carbon, can be purchased for less
than a dollar. Both items contain carbon, but there is a big difference in how that carbon is
organized. The diamond was formed under very different reaction conditions than the graphite,
so it has a different heat of formation.

Standard Heat of Formation

A relatively straightforward chemical reaction is one in which elements are combined to form a
compound. Sodium and chlorine react to form sodium chloride. Hydrogen and oxygen combine
to form water. Like other reactions, these are accompanied by either the absorption or release of
heat. The standard heat of formation (ΔHof)(ΔHfo) is the enthalpy change associated with
the formation of one mole of a compound from its elements in their standard states. The standard
conditions for thermochemistry are 25oC25oC and 101.3kPa101.3kPa. Therefore, the
standard state of an element is its state at 25oC25oC and 101.3kPa101.3kPa. For example,
iron is a solid, bromine is a liquid, and oxygen is a gas under those conditions. The standard heat
of formation of an element in its standard state by definition is equal to zero.
The ΔHof=0ΔHfo=0 for the diatomic
elements, H2(g)H2(g), N2(g)N2(g), O2(g)O2(g), F2(g)F2(g), Cl2(g)Cl2(g), Br2(g)Br2(g
), and I2(g)I2(g). The graphite form of solid carbon is in its standard state
with ΔHof=0ΔHfo=0, while diamond is not its standard state. Some standard heats of formation
are listed in the table below.

Summary
• The standard heat of formation (ΔHof)(ΔHfo) is the enthalpy change associated with the
formation of one mole of a compound from its elements in their standard states.
• The standard conditions for thermochemistry are 25oC25oC and 101.3kPa101.3kPa

17.17: Calculating Heat of Reaction from

Heat of Formation
Natural diamonds are mined from sites around the world. However, the price of natural
diamonds is carefully controlled, so other sources of diamonds are being explored. Several
different methods for producing synthetic diamonds are available, usually involving treating
carbon at very high temperatures and pressures. The diamonds produced are now of high quality,
but are primarily used in industrial applications. Diamonds are one of the hardest materials
available and are widely used for cutting and grinding tools.
 Calculating Heat of Reaction from Heat of
Formation
An application of Hess's law allows us to use standard heats of formation to indirectly calculate
the heat of reaction for any reaction that occurs at standard conditions. An enthalpy change that
occurs specifically under standard conditions is called the standard enthalpy (or heat) of
reaction and is given the symbol ΔHoΔHo. The standard heat of reaction can be calculated by
using the following equation.

ΔHo=∑nΔHof(products)−∑nΔHof(reactants)(17.17.1)

Table 17.17.117.17.1: Standard Heats of Formation of Select

Substance ΔHofΔHfo (kJ/mol)(kJ/mol) Substance

Al2O3(s)Al2O3(s) -1669.8 H2O2(l)H2O2(l)

BaCl2(s)BaCl2(s) -860.1 KCl(s)KCl(s)
Br2(g)Br2(g) 30.91 NH3(g)NH3(g)
C(s,graphite)C(s,graphite) 0 NO(g)NO(g)
C(s,diamond)C(s,diamond) 1.90 NO2(g)NO2(g)
CH4(g)CH4(g) -74.85 NaCl(s)NaCl(s)
C2H5OH(l)C2H5OH(l) -276.98 O3(g)O3(g)
CO(g)CO(g) -110.5 P(s,white)P(s,white)
CO2(g)CO2(g) -393.5 P(s,red)P(s,red)
CaO(s)CaO(s) -635.6 PbO(s)PbO(s)
CaCO3(s)CaCO3(s) -1206.9 S(rhombic)S(rhombic)
HCl(g)HCl(g) -92.3 S(monoclinic)S(monocli
CuO(s)CuO(s) -155.2 SO2(g)SO2(g)
CuSO4(s)CuSO4(s) -769.86 SO3(g)SO3(g)
Fe2O3(s)Fe2O3(s) -822.2 H2S(s)H2S(s)
H2O(g)H2O(g) -241.8 SiO2(s)SiO2(s)
H2O(l)H2O(l) -285.8 ZnCl2(s)ZnCl2(s)
The symbol Σ is the Greek letter sigma and means "the sum of". The standard heat of reaction is
equal to the sum of all the standard heats of formation of the products minus the sum of all the
standard heats of formation of the reactants. The symbol "nn" signifies that each heat of
formation must first be multiplied by its coefficient in the balanced equation.

Example 17.17.117.17.1
Calculate the standard heat of reaction (ΔHo)(ΔHo) for the reaction of nitrogen monoxide gas
with oxygen to form nitrogen dioxide gas.

Solution

Step 1: List the known quantities and plan the problem.

Known

• ΔHofΔHfo for NO(g)=90.4kJ/molNO(g)=90.4kJ/mol

• ΔHofΔHfo for O2(g)=0O2(g)=0 (element)
• ΔHofΔHfo for NO2(g)=33.85kJ/molNO2(g)=33.85kJ/mol

Unknown

• ΔHo=?kJΔHo=?kJ

First write the balanced equation for the reaction. Then apply the equation to calculate the
standard heat of reaction from the standard heats of formation.

Step 2: Solve.

The balanced equation is: 2NO(g)+O2(g)→2NO2(g)2NO(g)+O2(g)→2NO2(g)

Applying the equation from the text:

ΔHo=[2molNO2(33.85kJ/mol)]−[2molNO(90.4kJ/mol)+1molO2(0kJ/mol)]=−1
13kJ(17.17.2)(17.17.3)(17.17.2)ΔHo=[2molNO2(33.85kJ/mol)]−[2molNO(90.4kJ/mo
l)+1molO2(0kJ/mol)](17.17.3)=−113kJ

The standard heat of reaction is \(-113 \: \text{kJ}\]

Step 3: Think about your result.

The reaction is exothermic, which makes sense because it is a combustion reaction and combustion
reactions always release heat.

Summary
• An enthalpy change that occurs specifically under standard conditions is called the
standard enthalpy (or heat) of reaction and is given the symbol ΔHoΔHo.
• Standard heats of reaction can be calculated from standard heats of formation.