Slide 1

1) The magnitude of ΔH is proportional to the amount of reactant consumed in the process. When 1 mol
of CH4 is burned, 890 kJ of heat is produced. When 2 mol of CH4 is burned, 1780 kJ of heat is released.
2) When we reverse a reaction, we reverse the roles of the products and the reactants (i.e. the reactants
now become the products and the products become the reactants). Reversing the reaction leads to
the same magnitude of ΔH, but a change in sign. From (-) to (+) in our example.

Slide 2

Properties Enthalpy, h

The physical state of the reactants and products are very important in thermochemical equations. This is
because at different states, a substance will have a different enthalpy. If the H2O (l) in our example was
converted to H2O (g), the ΔH would have been -802 kJ since the enthalpy change of this particular reaction
is 88 kJ.
Slide 3

Because enthalpy is a state function, 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 final states 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.

As an example, the combustion of methane gas, CH4(g), to form CO2(g) and H2O(l) can be thought of as
occurring in one step. But this reaction can also be represented with 2 steps wherein the product of the
combustion of methane is H2O(g) and the 2nd step is the conversion of H2O(g) to H2O(l). For both processes,
whether one step or two steps, the net equation is the same and also the enthalpy change.

This is stated in Hess’s Law 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.” The enthalpy change is independent of
the number of steps and the path by which the reaction is carried out.

Slide 4

Different mechanisms or pathways can be used to reach a final equation, it may involve one step or a
series of steps, but as long as the final or net equations are the same, the ΔHrxn for all mechanisms would
be the same.
Slide 5

NOTE: Chemical equations are usually written with whole-number coefficients, but thermochemical
equations sometimes utilize fractions. Fractional coefficients are permissible in the latter to have the
smallest possible set of coefficients for a given reaction. If it were not used, the scale of the reaction or
the ΔH would be excessively large. However, interpret the coefficients as moles and not molecules.

A. Calculate the enthalpy for the combustion of C to CO. (1) and (2) are two thermochemical equations
and (3) is the final or the net equation. The ΔH of steps 1 and 2 are already given. The goal here is to
combine the two equations in such a way as to obtain the third equation and its enthalpy change.

A1. Compare equations 1 and 2 to equation 3. Identify the reactants and the products of (3) and locate
them at (1) and (2). Arrange (1) and (2) so that C(s) and ½ O2(g) are on the reactant side and CO(g)
is on the product side as in (3). Since (1) already has C(s) and ½ O 2(g) on the reactant side, so we
can use (1) as is.

A2. In (2), CO(g) is on the reactant side. Since we need it to be on the product side, we need to reverse
the equation. Recall one of the properties of enthalpy, that when we reverse the equation, the
magnitude of ΔH is the same but opposite sign. Turn (2) around and change the sign of ΔH to (+).

A3. When we add the equations, the substances common to both sides of the equation can be
cancelled out. CO2(g) appears on both sides of the equation, so it cancels out. Likewise, O2(g) is
cancelled and ½ O2(g) is left. Add the new ΔH of the (1) and (2) to get the final ΔH.

B. Calculate the ΔH for the conversion of graphite to diamond.

B1. The final equation has C(graphite) on the reactant and C(diamond) on the product. C(graphite) is
already on the reactant side on the first equation thus we will use it as is.

B2. Since C(diamond) is on the product side on the final equation, we have to turn around this
equation. When we turn this around, ΔH becomes (+).

B3. Because we turned the 2nd equation around, CO2(g) and O2(g) are now present on both sides of
the equation so they cancel out. The ΔHrxn is +1.9 kJ.
Slide 6

CALORIMETRY

Slide 7

▪Calorimetry
▪Heat Capacity
▪Specific Heat
OUTLINE ▪Types of Calorimetry
▪Hess’s Law
▪Enthalpies of Formation
▪Food and Fuels

Slide 8

The value of ∆H can be determined experimentally

by measuring the heat flow accompanying a reaction
at constant pressure.

▪ Calorimetry – measurement of heat flow

▪ Calorimeter – device used to measure heat flow
Slide 9

▪ The more heat an object gains, the hotter it gets.

▪ The magnitude of the temperature change varies
from substance to substance

▪ Heat Capacity, C – amount of heat required to raise

its temperature by 1 K (1°C).
*The greater heat capacity, the greater the heat
required to produce a given increase in temperature

All substances change temperature when they are heated, but the magnitude of the temperature
change produced by a given quantity of heat varies from substance to substance. For example,
object A and object B are both heated but the temperature of object A increased by 4 °C while
the temperature increase for object B is only 2 °C.

Heat capacity, C, is the amount of heat required to raise the temperature of an object by 1 K or
1 °C.

Slide 10

▪▪ Molar
Molar heat
heat capacity,
capacity,CCmm –– heat
heat capacity
capacity of
of one
one mole
mole of
of aa
substance
substance

▪▪ Specific
Specific heat,
heat,C
Css –– heat
heat capacity
capacity of
of one
one gram
gram of
of aa substance
substance
-- Can
Can be
be determined
determined experimentally
experimentally by
by measuring
measuring thethe
temperature
temperature change,
change,∆T,
∆T,that
that aa known
known mass
mass mm of
of the
the
substance undergoes when it gains or loses a specific
substance undergoes when it gains or loses a specific
quantity
quantity of
of heat
heat qq

Specific
Specific heat
heat ==

C
Css ==

Take note of the formula for Specific Heat, C s.

Slide 11

Cs =

Ex. 209 J is required to increase the temperature of

50.0 g of water by 1.00 K. What is its specific heat?

* ∆T in K = ∆T in °C

Because ΔT is just the difference of the final and initial temperatures, ΔT in K is the same with ΔT
in °C. For example, T1 = 298 K and T2 = 300 K, its ΔT = 2 K. Or T1 = 25 °C and T2 = 27 °C (same
temperature but in °C), its ΔT is also 2 °C. Use K when the required unit for the specific heat, C s,
is J/g·K or °C if J/g·°C.

The specific heat of water is 4.18 J/g·K.

Slide 12

When a sample absorbs heat (+q), its temperature

increases (+ ∆T), we get

q = Cs x m x ∆T
q = mC∆T

The specific heats for most substances are already known (Table 5.2). And we can use these pre-
determined values to calculate the quantity of heat a substance gains or loses together with its
measured mass and temperature change (q = mC ΔT read as “mCAT” for better recall). Notice
that the specific heat of liquid water is higher than those of the other substances listed. The high
specific heat of water affects Earth’s climate because it makes the temperatures of the oceans
relatively resistant to change.
Slide 13

Ex. a. How much heat is needed to warm 250 g of

water (about 1 cup) from 22 °C (about room temp) to
98 °C (near its boiling pt)? Cs H2O = 4.18 J/g-K

b. What is the molar heat capacity of water?

(Molar heat capacity, Cm – heat capacity of one mole
of a substance)

a. q = mC∆T
∆T = T2 – T1 = 98 °C – 22 °C = 76 °C
Since the Cs of H2O is in J/g-K, thus we will use ∆T = 76 K to cancel out the units.
q = mC∆T = (250g)(4.18 J/g-K)(76K) = 7.9 x 104 J

b. The Cs of H2O is in J/g-K and we want it now to be in J/mol-K, so we use the molar mass
of H2O to convert the grams to moles.
1 mol H2O = 18.0 g H2O
Cm = (4.18 J/g-K)(18 g/mol) = 75.2 J/mol-K
Slide 14

Constant-Pressure
Constant-PressureCalorimetry
Calorimetry
▪▪ No
Nophysical
physicalboundary
boundarybetween
betweenthe
thesystem
system
and
andthe
thesurroundings
surroundings
▪▪ The
Thereactants
reactantsand
andthe
theproducts
productsare
arethe
the
system
system
▪▪ The
Thewater
waterin
inwhich
whichthey
theyare
aredissolved
dissolvedis
ispart
part
of
ofthe
thesurroundings
surroundings (including
(includingthe
the
calorimeter
calorimeterapparatus)
apparatus)
▪▪ Assume
Assume that
thatcalorimeter
calorimeteris
isperfectly
perfectly
insulated:
insulated:any
anyheat
heatreleased
releasedor orabsorbed
absorbedbyby
the
thereaction
reactionwill
willraise
raiseor
orlower
lowerthe
the
temperature
temperatureofofthe
thewater
waterininthe
thesolution
solution
▪▪ Temperature
Temperaturechanges
changesare
aredue
dueto
toheat
heat
transferred
transferredfrom
fromthe
thereaction
reactionto
tothe
thewater
water
(exo)
(exo)or
ortransferred
transferredfrom
fromthe
thewater
waterto
tothe
the
reaction
reaction(endo).
(endo).

A simple “coffee-cup” calorimeter is often used in general chemistry laboratories to illustrate the
principles of calorimetry. Because the calorimeter is not sealed, the reaction occurs under the
essentially constant pressure of the atmosphere. Imagine adding two aqueous solutions, each
containing a reactant, to a coffee-cup calorimeter. Once mixed, a reaction occurs. Thus, there is
no physical boundary between the system and surroundings. By monitoring the temperature of
the solution, we are seeing the flow of heat between the system (the reactants and products in
the solution) and the surroundings (the water that forms the bulk of the solution).
Slide 15

Exothermic: heat is “lost” by the reaction (system)

and “gained” by the water (surrounding) so T rises

Endothermic: heat is “gained” by the reaction and

“lost” by the water in the solution, and T decreases

The heat gained or lost by the solution, qsoln, is equal

in magnitude but opposite in sign to the heat
absorbed or released by the reaction, qrxn.
qsoln = -qrxn

The value of qsoln is readily calculated from the mass of the solution, its specific heat, and the
temperature change: qsoln = (specific heat of solution) x (grams of solution) x ΔT = -qrxn

Slide 16

Therefore, qsoln = mC∆T = -qrxn

For dilute (aq) solutions, we assume that the Cs of the

solution is the same as that of water, 4.18 J/g-K.

We can calculate qrxn from temperature change. A

temperature increase (∆T > 0) means that the
exothermic
reaction is _________________ (qrxn < 0).
Slide 17

Ex. When 50.0 mL of 0.100 M AgNO3 and 50.0 mL of

0.100 M HCl are mixed in a constant-pressure
calorimeter, the temperature of the mixture increases
from 22.30 °C to 23.11 °C. The temperature increase
is caused by the following reaction:
AgNO3(aq) + HCl(aq) → AgCl(s) + HNO3(aq)

Calculate ∆H for this reaction in kJ/mol AgNO3,

assuming that the combined solution has a mass of
100.0 g and a specific heat of 4.18 J/g °C.

∆H = qp
qrxn = -mC∆T = -(100g)(4.18J/g-°C)(23.11°C -22.3°C) = -338.58 J = -0.33858 kJ
∆H = -0.33858 kJ
*0.100 M AgNO3 = 0.100 mol/L AgNO3
mol AgNO3 = (0.100 mol/L)(0.050 L) = 0.005 mol
∆H = -0.33858 kJ/0.005 mol = -67.7 kJ/mol

Slide 18

Bomb
BombCalorimetry
Calorimetry(Constant-Volume
(Constant-VolumeCalorimetry)
Calorimetry)
▪▪ Combustion
Combustion reactions
reactions –– aa
compound
compound reacts
reacts completely
completely with
with
excess oxygen
excess oxygen
▪▪ The
The combustion
combustion reaction
reaction is
is initiated
initiated
by
by passing
passing an an electrical
electrical current
current
through
through aa fine
fine wire
wire in
in contact
contact with
with
the sample. When the wire becomes
the sample. When the wire becomes
sufficiently
sufficiently hot,
hot,the
the sample
sample ignites.
ignites.

qqrxn = -C cal xx ∆T
rxn = -Ccal ∆T

where
whereCCcal is total heat capacity of the calorimeter
cal is total heat capacity of the calorimeter

An important type of reaction studied using calorimetry is combustion, in which a compound

reacts completely with excess oxygen. Combustion reactions are most accurately studied using a
bomb calorimeter. The substance to be studied is placed in a small cup within an insulated sealed
vessel called a bomb. The bomb has an inlet valve for adding oxygen and electrical leads for
initiating the reaction. The sample is placed in the bomb and the bomb is sealed and pressurized
with oxygen. This is then covered with an accurately measured quantity of water and the
combustion reaction is initiated. The heat released when combustion occurs is absorbed by the
water and the various components of the calorimeter (which all make up the surroundings),
causing the water temperature to rise. The ∆T of the water is measured very precisely.

Slide 19

The heat evolved in the reaction in a bomb calorimeter, qrxn = -Ccal x ∆T. Because reactions in a
bomb calorimeter are carried out at constant volume, the heat transferred corresponds to the
change in internal energy, ∆E, rather than the change in enthalpy, ∆H.

Sol’n: ∆T = 39.50 °C -25.00 °C = 14.50 °C

qrxn =-Ccal x ∆T = -(7.794 kJ/°C)(14.50 °C) = -113.0 kJ

Slide 20

Enthalpies
Enthalpiesof
ofFormation
Formation
▪▪ Enthalpy
Enthalpy change
change associated
associated with
with the
the process
process of
of formation
formation of
of aa
compound
compound (ex.
(ex.Enthalpies
Enthalpies ofof vaporization,
vaporization,fusion,
fusion,combustion,
combustion,etc.)
etc.)
▪▪ ∆H where f is formed from its constituent elements
∆Hff where f is formed from its constituent elements

▪▪ Standard
Standard enthalpy
enthalpy change
change –– enthalpy
enthalpy change
change when
when all
all the
the
reactants
reactants and
and products
products are
are in
in their
their standard
standard states
states (at
(at 25
25 °C,
°C,11 atm)
atm)
▪▪ ∆H° where ° indicates standard-state conditions
∆H° where ° indicates standard-state conditions

▪▪ Standard
Standard enthalpy
enthalpy of
of formation
formation –– change
change in
in enthalpy
enthalpy for
for the
the
reaction
reaction that
that forms
forms one
one mole
mole ofof the
the compound
compound from
from its
its elements
elements
with all substances in their standard states
with all substances in their standard states
▪▪∆H°
∆H°ff

Extensive tables exist of enthalpies of vaporization ( ∆H for converting liquids to gases), enthalpies of
fusion (∆H for melting solids), enthalpies of combustion (∆H for combusting a substance in
oxygen), and so forth. An important process is the formation of a compound from its constituent
elements. The enthalpy change associated with this process is called the enthalpy of formation
(or heat of formation). ∆Hf where f indicates that the substance has been formed from its
constituent elements.
The magnitude of any enthalpy change depends on the T, P, and state of the reactants and
products. To compare enthalpies of different reactions, we must define a set of conditions, called
a standard state. The standard state of a substance is at its pure form at 1 atm (1 bar for gases)
and 25 °C.
We denote a standard enthalpy change as ∆H°, where the superscript ° indicates standard-state
conditions, thus ∆H°f for the standard enthalpy of formation.
Slide 22

By convention, ∆H°f of an element = 0 because there is no formation

reaction needed when the element is already in its standard state.

If an element exists in more than one form under std conditions, the most stable form of the element is
usually used for the formation reaction. The elemental source of oxygen is O2, not O or O3, because O2 is
the stable form of oxygen at std conditions. Similarly, the elemental source of carbon is graphite and not
diamond because graphite is the more stable (lower-energy) form at std conditions. Likewise, H2(g) is the
most stable form of hydrogen. Table 5.3 shows some values of ∆H°f. By definition, the ∆H°f of the most
stable form of any element is zero because there is no formation reaction needed when the
element is already in its standard state. Thus, the values of ∆H° f for C(graphite), H2(g), O2(g), and
the std states of other elements are zero by definition.

Slide 23

NOTE: The ∆H°f is represented by a reaction in which

1) each reactant is an element in its standard state and
2) the product is one mole of the compound.

Which reaction (a to c) does the enthalpy change represent a standard enthalpy of formation, ∆H°f? The
∆H°f is represented by a reaction in which each reactant is an element in its standard state and
the product is one mole of the compound.
a. 1 mol Na2O (product) is formed from the elements Na and O2 in its proper states, thus ∆H°f.
b. 2 mol KCl (product) are formed so not ∆H°f. The ∆H°f should be K(s) + ½ Cl2(g) → KCl(s).
c. Not ∆H°f since the substance did not form from its elements. Instead, a substance
decomposes to its elements. The reaction should be reversed to represent ∆H°f.
Slide 24

Using Enthalpies of Formation to Calculate Enthalpies of Reaction

We can use Hess’ Law and tabulations of ∆H°f values to calculate the standard enthalpy change
for any reaction for which we know the ∆H°f values for all reactants and products. Take for
example the combustion of propane under std conditions (above).

The value of ∆H1, ∆H2, and ∆H3 are given in Tables. Using Hess’s Law and values of ∆H°f we can
calculate the ∆H°rxn. The ∆H°rxn = -2220 kJ represents the enthalpy change for the reaction of (1).

ADDITIONAL TOPICS (not included in the exam)

Slide 25

Food and Fuels

Most chemical reactions used for the production of heat are
combustion reactions

Fuel value – energy released when one gram of any substance is

combusted

The fuel value of any food or fuel can be measured by calorimetry

Most of the energy our bodies need comes from carbohydrates and
fats

Carbohydrates known as starches are decomposed in the intestines

into glucose, C6H12O6.
Fats produces CO2 and H2O when metabolized.
Slide 26

Combustion of Glucose, a simple carbohydrate

Combustion of Tristearin, a typical fat

The body uses chemical energy from foods to maintain body

temperature, to contract muscles, and to construct and repair tissues.
Any excess energy is stored as fats.

Fats are well suited to serve as the body’s energy reserve

1) They are insoluble in water, which facilitates storage in the body
2) They produce more energy per gram than either proteins or
carbohydrates; efficient energy sources on a mass basis

Slide 27

Combustion of carbohydrates and fats in a bomb calorimeter gives

the same products as when they are metabolized in the body.

However, the metabolism of proteins produces less energy than

combustion in a calorimeter because the products are different.
Proteins contain nitrogen, which is released in the bomb calorimeter
as N2. in the body this nitrogen ends up mainly as urea (NH2)2CO.

Proteins are used by the body mainly as building materials for organ
walls, skin, hair, muscle, and so forth.
Slide 28

The amount of energy our bodies require varies depending on factors as weight, age, muscular
activity. Which food gives you a high fuel value or energy? A combination of bread and cheese is
a good breakfast for energy. Fudge like Fudgee bar is a good source of energy too. Surprisingly,
peanuts are fully-packed. Consider snacking on peanuts if you want to pull an all-nighter. They
are good for the brain too. Beer? Does you no good. Just kidding.

Slide 29

A 100 kJ/kg of
body mass is
required to
keep the body
functioning at
minimal level.
An ave 70-kg
(154-lb)
person
expends about
800 kJ/hr
when doing
light work,
2000 kJ/hr for
strenuous
activity

Sample calculation on how much fuel value a food has and how much serving of it should you eat. You
can find the amount of proteins, carbohydrates, and fats at the back of food packaging (see Slide 6).
Slide 30

Fuels
During the complete combustion of fuels, carbon is converted to
CO2 and hydrogen is converted to H2O, both of which have large
negative enthalpies of formation.

The greater the percentage of carbon and hydrogen in a fuel, the

higher its fuel value.

In the table of some common fuels, Hydrogen has the highest fuel value.

Slide 31

Examples of fossil fuels (natural fuels):

Coal, petroleum, and natural gas

– world’s major sources of energy
- Formed over millions of years from the decomposition of plants
and animals

1) Natural Gas – gaseous hydrocarbons (methane, propane, butane)

2) Petroleum – a liquid composed of hundreds of compounds, most
of which are hydrocarbons, with the remainder being chiefly
organic compounds containing sulfur, nitrogen, or oxygen
3) Coal – solid which contains high molecular weight hydrocarbons
as well as compounds containing sulfur, oxygen and nitrogen; the
most abundant fossil fuel

Coal contains components that cause air pollution. S is converted to SO2 which is an air pollutant.

Fossil fuels release energy in combustion reactions and produce only CO 2 and H2O. The
production of CO2 has become a major issue that involves science and public policy because of
concerns that increasing concentrations of CO2 are causing global climate changes.
Slide 32

Other Energy Sources

1) Nuclear energy – energy released in either the splitting or the
fusion of atomic nuclei

• Fossil fuel and nuclear energy are nonrenewable energy sources

Renewable Energy Sources:

1) Solar energy – from the Sun

2) Wind energy – harnessed by windmills
3) Geothermal energy – from the heat stored inside Earth
4) Hydroelectric energy – from flowing rivers
5) Biomass energy – from crops and biological waste matter

Nuclear energy is free of polluting emissions but nuclear plants produce radioactive waste
products.

There are also alternative energy sources. Which do you think is the most sustainable, safe,
economical renewable energy souce?