Thermochemistry: Lecture Presentation

Lecture Presentation
Chapter 5
Thermochemistry
James F. Kirby
Quinnipiac University
Hamden, CT
© 2018 Pearson Education, Inc.
Energy
• From Chapter 1, energy is the ability to do work

or transfer heat.
• This chapter is about thermodynamics, which is
the study of energy and its transformations.
• Specifically, thermochemistry is the study of
chemical reactions and the energy changes that
involve heat.
Thermochemistry

Energy
• Definitions:
– Energy is the capacity to do work or to transfer heat.
– Work is energy used to cause an object with mass to
move.
• w = F × d ; F is the force, and d is the distance over which the
force is exerted.
• A force is any kind of push or pull exerted on an object.
• The most familiar force is the pull of gravity.
– Heat is the energy used to cause the temperature of
an object to increase.
• Heat flows from warmer objects to cooler objects.
Thermochemistry

Kinetic Energy
• Kinetic energy is energy an object
possesses by virtue of its motion:
1
Ek =  mv2
2
Thermochemistry

Chemical Energy is
Mainly Potential Energy
• Potential energy is
energy an object
possesses by virtue of
its position or chemical
composition
• The most important form
of potential energy in
molecules is electrostatic
potential energy, Eel:
• Q = electric charge Thermochemistry

Units of Energy
• The SI unit of energy is the joule (J):

kg m2
1 J = 1 
s2
• An older, non-SI unit is still in widespread
use: the calorie (cal):
1 cal = 4.184 J
Thermochemistry

Attraction between Ions
• Electrostatic attraction is
seen between
oppositely charged ions.
• Energy is released
when chemical bonds
are formed; energy is
consumed when
chemical bonds are
broken.
Thermochemistry

Definitions: System and Surroundings
• The portion of the

universe that we single
out to study is called the
system (here, the
hydrogen and oxygen
molecules).
• The surroundings are
everything else (here, the
cylinder, piston and
everything beyond).
Thermochemistry

Types of Systems
1) Open System: a region of the
universe being studied that
can exchange heat AND mass
with its surroundings.
2) Closed System: a region of
the universe being studied
that can ONLY exchange
heat with its surroundings
(NOT mass)
3) Isolated System: a region of Note that this is a
the universe that can NOT CLOSED system.
exchange heat or mass with
its surroundings Thermochemistry

First Law of Thermodynamics
• Energy can be converted from one form to
another, but it is neither created nor destroyed.
• To heat your home, chemical energy needs to
be converted to heat.
• Sunlight is converted to chemical energy in
green plants.
• There are MANY more examples of
conversion of energy.
Thermochemistry

Conversion of Energy
• Energy can be converted from one type to

another.
• For example, the cyclist has potential energy
as she sits on top of the hill.
Thermochemistry

Conversion of Energy
• As she coasts down the hill, her potential

energy is converted to kinetic energy.
• At the bottom, all the potential energy she
had at the top of the hill is now kinetic energy.
Thermochemistry

Internal Energy
• The internal energy of a system is the sum of all
kinetic and potential energies of all components
of the system; we use E to represent it.
• We generally don’t know E, only how it
CHANGES (ΔE).
Thermochemistry

Internal Energy
• By definition, the change in
internal energy, ΔE, is the final
energy of the system minus the
initial energy of the system:
• ΔE = Efinal − Einitial
• If: ΔE > 0, Efinal > Einitial
– the system absorbed energy from
the surroundings; endergonic
• If: ΔE < 0, Efinal < Einitial
– the system released energy to the
surroundings; exegornic
Thermochemistry

Thermodynamic Quantities
Have Three Parts
1) A number
2) A unit
3) A sign
Note about the sign:
– A positive ΔE (endergonic) results when the
system gains energy from the surroundings.
– A negative ΔE (exegornic) results when the
system loses energy to the surroundings.
Thermochemistry

Changes in Internal Energy
• When energy is
exchanged between
the system and the
surroundings, it is
exchanged as either
heat (q) or work (w).
• That is, ΔE = q + w.
Thermochemistry

ΔE, q, w, and Their Signs
Thermochemistry

Exchange of Heat between System and
Surroundings
• When heat is absorbed by the system from the
surroundings, the process is endothermic (
흡열반응 ).
Thermochemistry

Exchange of Heat between System and
Surroundings
• When heat is released by the system into
the surroundings, the process is exothermic
( 발열반응 ).
Thermochemistry

Sample Exercise 5.1 Relating Heat and Work to Changes of Internal
Energy
Gases A(g) and B(g) are confined in a cylinder-and-piston arrangement like that in Figure 5.4 and react to form a solid
product C(s): A(g) + B(g) C(s). As the reaction occurs, the system loses 1150 J of heat to the surroundings. The
piston moves downward as the gases react to form a solid. As the volume of the gas decreases under the constant
pressure of the atmosphere, the surroundings do 480 J of work on the system. What is the change in the internal energy
of the system?
Solution
Analyze The question asks us to determine E, given information about q and w.
Plan We first determine the signs of q and w (Table 5.1) and then use Equation 5.4, E = q + w, to calculate E.
Solve Heat is transferred from the system to the surroundings, and work is done on the system by the surroundings,
so q is negative and w is positive: q = –1150 J and w = 480 J. Thus,
E = q + w = (–1150 J) + (480 J) = –670 J
The negative value of E tells us that a net quantity of 670 J of energy has been transferred from the system to the
surroundings.
Thermochemistry

State Functions
• Usually we have no way of knowing the internal energy of
a system; finding that value is simply too complex a
problem.
• However, we do know that the internal energy of a system
is independent of the path by which the system achieved
that state.
– In the system below, the water could have reached room
temperature from either direction.
Thermochemistry

State Functions
• Therefore, internal energy is a state function (
상태함수 ).
• It depends only on the present state of the
system, not on the path by which the system
arrived at that state.
• And so, ΔE depends only on Einitial and Efinal.
Thermochemistry

State Functions
• However, q and w are

not state functions:
path function
• Whether the battery is
shorted out or is
discharged by running
the fan, its ΔE is the
same,
– but q and w are
different in the two
cases.
Thermochemistry

State Functions vs Path Functions
A state function is a property describes a particular state, without
depending on the path taken to reach this state. In contrast, functions
whose value depends on the path taken to get between two states are
called path functions.
To understand the difference between the two, think of two cities, A and B,
that are 100km away from each other along a straight line. Roads are
rarely built in long straight lines, we may have two roads linking A and B,
with lengths 150km and 200km.
So, while the displacement between the two towns
is the same for each route (it is a state function),
the distance you need to travel to get from A to
B depends on which road you take (it is a path
function).
Both path and state functions are often encountered in thermodynamics.

Thermochemistry

Work
• We can measure the work done by the gas if the
reaction is done in a vessel that has been fitted
with a piston: w = −PΔV
• The work is NEGATIVE because it is work done
BY the system.
Thermochemistry

Sample Exercise 5.2 Calculating Pressure-Volume Work
A fuel is burned in a cylinder equipped with a piston. The initial volume of the cylinder is 0.250 L, and the final
volume is 0.980 L. If the piston expands against a constant pressure of 1.35 atm, how much work (in J) is done?
(1 L-atm = 101.3 J)
Solution
Analyze We are given an initial volume and a final volume from which we can calculate V. We are also given the
pressure, P. We are asked to calculate work, w.
Plan The equation w = –PV allows us to calculate the work done by the system from the given information.
Solve The volume change is
V = Vfinal – Vinitial = 0.980 L – 0.250 L = 0.730 L
Thus, the quantity of work is
w = –PV = –(1.35 atm)(0.730 L) = –0.9855 L-atm
Converting L-atm to J, we have
Thermochemistry

Enthalpy
• Chemical and physical changes that occur
around us occur under essentially constant
pressure of Earth’s atmosphere.
– Changes may be accompanied by work done by or
on the system.
– Changes may involve the release or absorption of
heat.
– We will focus much of our discussion on what we can
learn from measurement of heat flow.
Thermochemistry

Enthalpy
• Enthalpy (H) is defined as the internal energy

(E) plus the product of the pressure and volume
of the system.
• H = E + PV
• Enthalpy is useful for investigating heat flow in
events that occur under constant pressure.
• Again, we can only measure the change in
enthalpy, ΔH. H is state function?
Thermochemistry

Enthalpy
• ΔH = Hfinal – Hinitial = ΔE + PΔV (constant pressure)
• w = –PΔV; ΔE = q + w
• ΔH = ΔE + PΔV = (qp + w) – w = qp
• For most reactions, PΔV is small thus ΔH = ΔE
• Heat transferred from surroundings to the system has a
positive enthalpy (i.e., ΔH > 0 for an endothermic
reaction).
• Heat transferred from the system to the surroundings
has a negative enthalpy (i.e., ΔH < 0 for an exothermic
reaction).
• Enthalpy is a state function.
Thermochemistry

Endothermic and Exothermic
• 앞에서 ΔE 에 대한
것과 마찬가지로 ΔH
에 적용해 보면 ,
• A process is
endothermic when
ΔH is positive.
• A process is
exothermic when
ΔH is negative.
Thermochemistry

Sample Exercise 5.3 Determining the Sign of H
Indicate the sign of the enthalpy change, H, in the following processes carried out under atmospheric pressure
and indicate whether each process is endothermic or exothermic: (a) An ice cube melts; (b) 1 g of butane
(C4H10) is combusted in sufficient oxygen to give complete combustion to CO 2 and H2O.
Solution
Analyze Our goal is to determine whether H is positive or negative for each process. Because each process occurs at
constant pressure, the enthalpy change equals the quantity of heat absorbed or released, H = qP.
Plan We must predict whether heat is absorbed or released by the system in each process. Processes in which heat is
absorbed are endothermic and have a positive sign for H; those in which heat is released are exothermic and have a
negative sign for H.
Solve In (a) the water that makes up the ice cube is the system. The ice cube absorbs heat from the surroundings as it
melts, so H is positive and the process is endothermic. In (b) the system is the 1 g of butane and the oxygen required
to combust it. The combustion of butane in oxygen gives off heat, so H is negative and the process is exothermic.
Practice Exercise 1
A chemical reaction that gives off heat to its surroundings is said to be _________ and has a _________ value of H.
(a) endothermic, positive (b) endothermic, negative (c) exothermic, positive (d) exothermic, negative
Practice Exercise 2
Molten gold poured into a mold solidifies at atmospheric pressure. With the gold defined as the system, is the
solidification an exothermic or endothermic process? Thermochemistry

Work
• Usually the only

work done by
chemical or
physical change
is the mechanical
work associated
with a change in
volume of gas.
Thermochemistry

Work
• A cylinder of cross-sectional area A,
• A piston exerting a pressure, P = F/A, on a gas inside the
cylinder,
• The volume of gas expanding through ΔV while the piston
moves a height Δh = hf – hi.
• The magnitude of work done = F × Δh = P × A × Δh = P × ΔV.
• Since work is being done by the system on the surroundings,
– w = –PΔV.
• Using the first law of thermodynamics,
– ΔE = q – PΔV.
• If the reaction is carried out under constant volume,
– ΔV = 0 and ΔE = qv. - ΔH = ΔE + PΔV = (qp + w) – w = qp
Thermochemistry

Enthalpy of Reaction
The change in
enthalpy, ΔH, is the
enthalpy of the
products minus the
enthalpy of the
reactants:
ΔHrxn = Hproducts − Hreactants
Thermochemistry

The Truth about Enthalpy
1. Enthalpy is an extensive property: Therefore,

the magnitude of enthalpy is directly
proportional to the amount of reactant
consumed.
2. H for a reaction in the forward direction is
equal in size, but opposite in sign, to H for
the reverse reaction.
3. H for a reaction depends on the state of the
products and the state of the reactants;
2H2O(g) → 2H2O(l) ΔH = –88 kJ
Thermochemistry

This quantity, ΔHrxn, is called the enthalpy of
reaction, or the heat of reaction.
Thermochemistry

Sample Exercise 5.4 Relating H to Quantities of Reactants and
Products
How much heat is released when 4.50 g of methane gas is burned in a constant-pressure system? (Use the information
given in Equation 5.17.)
Solution
Analyze Our goal is to use a thermochemical equation to calculate the heat produced when a specific amount of
methane gas is combusted. According to Equation 5.17, 890 kJ is released by the system when 1 mol CH 4 is burned
at constant pressure.
Plan Equation 5.17 provides us with a stoichiometric conversion factor: (1 mol CH4 –890 kJ). Thus, we can
convert moles of CH4 to kJ of energy. First, however, we must convert grams of CH4 to moles of CH4.
Solve
The conversion sequence is:
By adding the atomic weights of C and 4 H, we have

1 mol CH4 = 16.0 CH4. We can use the appropriate
conversion factors to convert grams of CH4 to moles The negative sign indicates that the system
of CH4 to kilojoules: released 250 kJ into the surroundings.
Thermochemistry

Calorimetry
• Since we cannot know the

exact enthalpy of the
reactants and products,
we measure ΔH through
calorimetry, the
measurement of heat flow.
• The instrument used to
measure heat flow is
called a calorimeter.
Thermochemistry

Heat Capacity and Specific Heat
• The amount of energy required to raise the
temperature of a substance by 1 K (1C) is its
heat capacity.
– Molar heat capacity is the heat capacity of 1 mol of a
substance.
– Specific heat, or specific heat capacity, is the heat
capacity of 1 g of a substance.
Thermochemistry

Heat Capacity and Specific Heat
Specific heat, then, is
heat transferred
Specific heat =
mass  temperature change
q
Cs =
m  T
q = Cs  m  T
Thermochemistry

Sample Exercise 5.5 Relating Heat, Temperature Change, and Heat
Capacity
(a) How much heat is needed to warm 250 g of water (about 1 cup) from 22 °C (about room temperature) to 98 °C
(near its boiling point)? (b) What is the molar heat capacity of water?
Solution
Analyze In part (a) we must find the quantity of heat (q) needed to warm the water, given the mass of
water (m), its temperature change (T ), and its specific heat (Cs). In part (b) we must calculate the molar heat
capacity (heat capacity per mole, Cm) of water from its specific heat (heat capacity per gram).
Plan (a) Given Cs, m, and T, we can calculate the quantity of heat, q, using Equation 5.21. (b) We can use the molar
mass of water and dimensional analysis to convert from heat capacity per gram to heat capacity per mole.
Solve
(a) The water undergoes a temperature change of: T = 98 °C – 22 °C = 76 °C = 76 K
Using Equation 5.21, we have:
(b) The molar heat capacity is the heat capacity of one mole of substance. Using the atomic weights of hydrogen and
oxygen, we have:
1 mol H2O = 18.0 g H2O

Thermochemistry

Sample Exercise 5.5 Relating Heat, Temperature Change, and Heat
Capacity
Continued
From the specific heat used in part (a), we have
Practice Exercise 1
The coinage metals (Group 1B) copper, silver, and gold have specific heats of 0.385, 0.233, and 0.129 J/g-K,
respectively. Among this group, the specific heat capacity __________ and the molar heat capacity __________ as
the atomic weight increases. (a) increases, increases (b) increases, decreases (c) decreases, increases (d) decreases,
decreases
Practice Exercise 2
(a) Large beds of rocks are used in some solar-heated homes to store heat. Assume that the specific heat of the rocks
is 0.82 J/g-K. Calculate the quantity of heat absorbed by 50.0 kg of rocks if their temperature increases by 12.0 °C.
(b) What temperature change would these rocks undergo if they emitted 450 kJ of heat?
Thermochemistry

Constant Pressure Calorimetry
• By carrying out a reaction in aqueous
solution in a simple calorimeter, the
heat change for the system can be
found by measuring the heat change
for the water in the calorimeter; qp.
• The specific heat for water is
4.184 J/g∙K. We use this value for
dilute solutions.
• We can calculate ΔH for the reaction
with this equation:
qsoln, p = Cs × msoln × ΔT = –qrxn
Thermochemistry

Sample Exercise 5.6 Measuring H Using a Coffee-Cup Calorimeter
When a student mixes 50 mL of 1.0 M HCl and 50 mL of 1.0 M NaOH in a coffee-cup calorimeter, the temperature of
the resultant solution increases from 21.0 to 27.5 °C. Calculate the enthalpy change for the reaction in kJ/mol HCl,
assuming that the calorimeter loses only a negligible quantity of heat, that the total volume of the solution is 100 mL,
that its density is 1.0 g/mL, and that its specific heat is 4.18 J/g-K.
Solution
Analyze Mixing solutions of HCl and NaOH results in an acid-base reaction:
HCl(aq) + NaOH(aq) H2O(l) + NaCl(aq)
We need to calculate the heat produced per mole of HCl, given the temperature increase of the solution, the number of
moles of HCl and NaOH involved, and the density and specific heat of the solution.
Plan The total heat produced can be calculated using Equation 5.22. The number of moles of HCl consumed in the
reaction must be calculated from the volume and molarity of this substance, and this amount is then used to determine
the heat produced per mol HCl.
Solve
Because the total volume of the solution is 100 mL, its mass is: (100 mL)(1.0 g/mL) = 100 g
The temperature change is: T = 27.5 °C – 21.0 °C = 6.5 °C = 6.5 K
Using Equation 5.22, we have:
Thermochemistry

Sample Exercise 5.6 Measuring H Using a Coffee-Cup Calorimeter
Continued
Because the process occurs at constant pressure, H = qP = –2.7 kJ
To express the enthalpy change on a molar basis, we use the

fact that the number of moles of HCl is given by the product
of the volume (50 mL = 0.050 L) and concentration
(1.0 M = 1.0 mol/L) of the HCl solution:
Thus, the enthalpy change per mole of HCl is: H = –2.7 kJ/0.050 mol = –54 kJ/mol
Check H is negative (exothermic), as evidenced by the observed increase in the temperature. The magnitude of the
molar enthalpy change seems reasonable.
Practice Exercise 1
When 0.243 g of Mg metal is combined with enough HCl to make 100 mL of solution in a constant-pressure
calorimeter, the following reaction occurs:
Mg(s) + 2 HCl(aq) MgCl2(aq) + H2(g)
If the temperature of the solution increases from 23.0 to 34.1 °C as a result of this reaction, calculate H in kJ/mol Mg.
Assume that the solution has a specific heat of 4.18 J/g-°C and a density of 1.00 g/mL. (a) –19.1 kJ/mol
(b) –111 kJ/mol (c) –191 kJ/mol (d) –464 kJ/mol (e) –961 kJ/mol
Thermochemistry

Bomb Calorimetry
• Reactions can be carried out
in a sealed “bomb”
such as this one.
• The heat absorbed (or
released) by the water is
a very good approximation of
the enthalpy change for the
reaction: heat of combustion.
• Qv,rxn = – Ccal × ΔT
Thermochemistry

Bomb Calorimetry
• The most common type of reaction studied
under these conditions is combustion.
• If we know the heat capacity of the
calorimeter, Ccal, then the heat of reaction,
• qrxn = –Ccal × ΔT.
• Because the volume in the bomb calorimeter
is constant, what is measured is really the
change in internal energy, E = qv, not H.
• For most reactions, the difference is very
small. Thermochemistry

Constant-Pressure vs. Constant-Volume
Calorimetry
Constant-Pressure Constant-Volume
Heat of reaction is equal to Heat of reaction is equal to

the enthalpy change the internal energy change
(open system) (closed system)
- ΔH = qp = ΔE + PΔV qv = ΔE + PΔV(0) = ΔE
q = CsmΔT q = CcalΔT
Calorimeter “coffee cup” Bomb Calorimeter

Thermochemistry

Sample Exercise 5.7 Measuring qrxn Using a Bomb Calorimeter
The combustion of methylhydrazine (CH6N2), a liquid rocket fuel, produces N2(g), CO2(g), and H2O(l):
2 CH6N2(l) + 5 O2(g) 2 N2(g) + 2 CO2(g) + 6 H2O(l)
When 4.00 g of methylhydrazine is combusted in a bomb calorimeter, the temperature of the calorimeter increases
from 25.00 to 39.50 °C. In a separate experiment the heat capacity of the calorimeter is measured to be 7.794 kJ/°C.
Calculate the heat of reaction for the combustion of a mole of CH6N2.
Solution
Analyze We are given a temperature change and the total heat capacity of the calorimeter. We are also given the
amount of reactant combusted. Our goal is to calculate the enthalpy change per mole for combustion of the reactant.
Plan We will first calculate the heat evolved for the combustion of the 4.00-g sample. We will then convert this heat to
a molar quantity.
Solve
For combustion of the 4.00-g sample of methylhydrazine, the temperature change of the calorimeter is:
T = (39.50 °C – 25.00 °C) = 14.50 °C
We can use T and the value for Ccal to calculate the heat of reaction (Equation 5.23):
Thermochemistry

Sample Exercise 5.7 Measuring qrxn Using a Bomb Calorimeter
Continued
We can readily convert this value to the heat of reaction for a mole of CH6N2:
Check The units cancel properly, and the sign of the answer is negative as it should be for an exothermic reaction. The
magnitude of the answer seems reasonable.
Practice Exercise 1
The combustion of exactly 1.000 g of benzoic acid in a bomb calorimeter releases 26.38 kJ of heat. If the combustion
of 0.550 g of benzoic acid causes the temperature of the calorimeter to increase from 22.01 to 24.27 °C, calculate the
heat capacity of the calorimeter. (a) 0.660 kJ/°C (b) 6.42 kJ/°C (c) 14.5 kJ/°C (d) 21.2 kJ/g-°C (e) 32.7 kJ/°C
Practice Exercise 2
A 0.5865-g sample of lactic acid (HC3H5O3) reacts with oxygen in a calorimeter whose heat capacity is 4.812 kJ/°C.
The temperature increases from 23.10 to 24.95 °C. Calculate the heat of combustion of lactic acid (a) per gram and
(b) per mole.
Thermochemistry

Hess’s Law
• ΔH is well known for many reactions, and it

is inconvenient to measure ΔH for every
reaction in which we are interested.
• However, we can calculate ΔH for a
reaction using published ΔH values and the
properties of enthalpy.
Thermochemistry

Hess’s Law
• Hess’s law: 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.
• Because H is a state function, for a particular set of
reactants and products, ΔH is the same whether the
reaction takes place in one step or in a series of
steps.
Thermochemistry

Sample Exercise 5.8 Using Hess’s Law to Calculate H
The enthalpy of reaction for the combustion of C to CO2 is –393.5 kJ/mol C, and the enthalpy for the combustion of
CO to CO2 is –283.0 kJ/mol CO:
(1) C(s) + O2(g) CO2(g) H = –393.5 kJ
(2) CO(g) + O2(g) CO2(g) H = –283.0 kJ
Using these data, calculate the enthalpy for the combustion of C to CO:
(3) C(s) + O2(g) CO(g) H = ?
Solution
Analyze We are given two thermochemical equations, and our goal is to combine them in such a way as to obtain the
third equation and its enthalpy change.
Plan We will use Hess’s law. In doing so, we first note the number of moles of substances among the reactants and
products in the target equation (3). We then manipulate equations (1) and (2) to give the same number of moles of
these substances, so that when the resulting equations are added, we obtain the target equation. At the same time, we
keep track of the enthalpy changes, which we add.
Thermochemistry

Sample Exercise 5.8 Using Hess’s Law to Calculate H
Continued
Solve To use equations (1) and (2), we arrange them so that C(s) is on the reactant side and CO(g) is on the product
side of the arrow, as in the target reaction, equation (3). Because equation (1) has C(s) as a reactant, we can use that
equation just as it is. We need to turn equation (2) around, however, so that CO(g) is a product. Remember that when
reactions are turned around, the sign of H is reversed. We arrange the two equations so that they can be added to give
the desired equation:
When we add the two equations, CO2(g) appears on both sides of the arrow and therefore cancels out. Likewise,
O2(g) is eliminated from each side.
Practice Exercise 1
Calculate H for 2 NO(g) + O2(g) N2O4(g), using the following information:
N2O4(g) 2 NO2(g) H = +57.9 kJ
2 NO(g) + O2(g) 2 NO2(g) H = –113.1 kJ
(a) 2.7 kJ (b) –55.2 kJ (c) –85.5 kJ (d) –171.0 kJ (e) +55.2 kJ
Thermochemistry

Sample Exercise 5.9 Using Hess’s Law with Three Equations to
Calculate H
Calculate H for the reaction
2 C(s) + H2(g) C2H2(g)
given the following chemical equations and their respective enthalpy changes:
C2H2(g) + O2(g) 2 CO2(g) + H2O(l) H = –1299.6 kJ
C(s) + O2(g) CO2(g) H = –393.5 kJ
H2(g) + O2(g) H2O(l) H = –285.8 kJ
Solution
Analyze We are given a chemical equation and asked to calculate its H using three chemical equations and their
associated enthalpy changes.
Plan We will use Hess’s law, summing the three equations or their reverses and multiplying each by an appropriate
coefficient so that they add to give the net equation for the reaction of interest. At the same time, we keep track of the
H values, reversing their signs if the reactions are reversed and multiplying them by whatever coefficient is
employed in the equation.
Thermochemistry

Sample Exercise 5.9 Using Hess’s Law with Three Equations to
Calculate H
Continued
Solve Because the target equation has C2H2 as a product, we turn the first equation around; the sign of H is therefore
changed. The desired equation has 2 C(s) as a reactant, so we multiply the second equation and its H by 2. Because
the target equation has H2 as a reactant, we keep the third equation as it is. We then add the three equations and their
enthalpy changes in accordance with Hess’s law:
When the equations are added, there are 2 CO2, O2, and H2O on both sides of the arrow. These are canceled in
writing the net equation.
Check The procedure must be correct because we obtained the correct net equation. In cases like this, you should
go back over the numerical manipulations of the H values to ensure that you did not make an inadvertent error
with signs.
Thermochemistry

Enthalpies of Formation
• If a compound is formed from its constituent

elements, then the enthalpy change for the
reaction is called the enthalpy of formation,
ΔHf.
• Standard state (standard conditions) refer to
the substance at: 1 atm and 25oC (298 K).
• Standard enthalpy, ΔHo, is the enthalpy
measured when everything is in its standard
state.
Thermochemistry

Standard Enthalpies of Formation
• Standard enthalpy of formation of a
compound, ΔHof, is the enthalpy change for the
formation of 1 mol of compound with all
substances in their standard states.
– A large majority of ΔHof values are negative, meaning
that most formation reactions are exothermic.
• If there is more than one state for a substance
under standard conditions, the more stable one
is used; When dealing with carbon we use graphite
because graphite is more stable than diamond.
• The standard enthalpy of formation of the most
stable form of an element is zero. Thermochemistry

Standard Enthalpies of Formation
Thermochemistry

Sample Exercise 5.10 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 H is an enthalpy of formation?
(a) 2 Na(s) + 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)
Solution
Analyze The standard enthalpy of formation 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.
Plan We need to examine each equation to determine (1) whether the reaction is one in which one mole of substance is
formed from the elements, and (2) whether the reactant elements are in their standard states.
Solve In (a) 1 mol Na2O is formed from the elements sodium and oxygen in their proper states, solid Na and O2 gas,
respectively. Therefore, the enthalpy change for reaction (a) corresponds to a standard enthalpy of formation.
In (b) potassium is given as a liquid. It must be changed to the solid form, its standard state at room temperature.
Furthermore, 2 mol KCl are formed, so the enthalpy change for the reaction as written is twice the standard enthalpy of
formation of KCl(s). The equation for the formation reaction of 1 mol of KCl(s) is
K(s) + Cl2(g) KCl(s)

Thermochemistry

Sample Exercise 5.10 Equations Associated with Enthalpies of
Formation
Continued
Reaction (c) does not form a substance from its elements. Instead, a substance decomposes to its elements, so this
reaction must be reversed. Next, the element carbon is given as diamond, whereas graphite is the standard state of
carbon at room temperature and 1 atm pressure. The equation that correctly represents the enthalpy of formation of
glucose from its elements is
6 C(graphite) + 6 H2(g) + 3 O2(g) C6H12O6(s)
Practice Exercise 1
If the heat of formation of H2O(l) is –286 kJ/mol, which of the following thermochemical equations is correct?
(a) 2 H(g) + O(g) H2O(l) H = –286 kJ
(b) 2 H2(g) + O2(g) 2 H2O(l) H = –286 kJ
(c) H2(g) + O2(g) H2O(l) H = –286 kJ
(d) H2(g) + O(g) H2O(g) H = –286 kJ
(e) H2O(l) H2(g) + O2(g) H = –286 kJ
Practice Exercise 2
Write the equation corresponding to the standard enthalpy of formation of liquid carbon tetrachloride (CCl 4) and look
up for this compound in Appendix C.
Thermochemistry

Calculation of ΔH
C3H8(g) + 5 O2(g) 3 CO2(g) + 4 H2O(l)
• The sum of these

equations is the overall
equation!
C3H8(g) 3 C(graphite) + 4 H2(g)

3 C(graphite) + 3 O2(g) 3 CO2(g)
4 H2(g) + 2 O2(g) 4 H2O(l)
C3H8(g) + 5 O2(g) 3 CO2(g) + 4 H2O(l) Thermochemistry

Calculation of ΔH
We can use Hess’s law in this way:
ΔH = ΣnΔHf°,products – ΣmΔHf°,reactants
where n and m are the stoichiometric

coefficients.
Thermochemistry

Calculation of ΔH using Values from the
Standard Enthalpy Table
C3H8(g) + 5 O2(g) 3 CO2(g) + 4 H2O(l)
ΔH = [3(−393.5 kJ) + 4(−285.8 kJ)] – [1(−103.85 kJ) + 5(0
kJ)]
= [(−1180.5 kJ) + (−1143.2 kJ)] – [(−103.85 kJ) + (0 kJ)]
= (−2323.7 kJ) – (−103.85 kJ) = −2219.9 kJ
Thermochemistry

Sample Exercise 5.11 Calculating an Enthalpy of Reaction from
(a) Calculate the standard enthalpy change for the combustion of 1 mol of benzene, C 6H6(l), to CO2(g) and H2O(l).
(b) Compare the quantity of heat produced by combustion of 1.00 g propane with that produced by 1.00 g benzene.
Solution
Analyze (a) We are given a reaction [combustion of C6H6(l) to form CO2(g) and H2O(l)] and asked to calculate its
standard enthalpy change, H°. (b) We then need to compare the quantity of heat produced by combustion of 1.00 g
C6H6 with that produced by 1.00 g C3H8, whose combustion was treated previously in the text. (See Equations 5.29 and
5.30.)
Plan (a) We first write the balanced equation for the combustion of C 6H6. We then look up values in Appendix C
or in Table 5.3 and apply Equation 5.31 to calculate the enthalpy change for the reaction. (b) We use the molar mass of
C6H6 to change the enthalpy change per mole to that per gram. We similarly use the molar mass of C 3H8 and the
enthalpy change per mole calculated in the text previously to calculate the enthalpy change per gram of that substance.
Thermochemistry

Continued
Solve
(a) We know that a combustion reaction involves O2(g) as a reactant. Thus, the balanced equation for the combustion
reaction of 1 mol C6H6(l) is: C6H6(l) + O2(g) 6 CO2(g) + 3 H2O(l)
We can calculate H° for this reaction by using Equation 5.31 and data in Table 5.3. Remember to multiply the
value for each substance in the reaction by that substance’s stoichiometric coefficient. Recall also that
= 0 for any element in its most stable form under standard conditions, so [O 2(g)] = 0.
(b) From the example worked in the text, H° = –2220 kJ for the combustion of 1 mol of propane. In part (a) of this
exercise we determined that H° = –3267 kJ for the combustion of 1 mol benzene. To determine the heat of
combustion per gram of each substance, we use the molar masses to convert moles to grams:
Thermochemistry

Continued
Comment Both propane and benzene are hydrocarbons. As a rule, the energy obtained from the combustion of a gram
of hydrocarbon is between 40 and 50 kJ.
Practice Exercise 1
Calculate the enthalpy change for the reaction
2 H2O2(l) 2 H2O(l) + O2(g)
using enthalpies of formation:
[H2O2(l)] = –187.8 kJ/mol [H2O(l)] = –285.8 kJ/mol
(a) –88.0 kJ
(b) –196.0 kJ
(c) +88.0 kJ
(d) +196.0 kJ
(e) more information needed
Practice Exercise 2
Use Table 5.3 to calculate the enthalpy change for the combustion of 1 mol of ethanol:
C2H5OH(l) + 3 O2(g) 2 CO2(g) + 3 H2O(l)

Thermochemistry

Sample Exercise 5.12 Calculating an Enthalpy of Formation Using
an Enthalpy of Reaction
The standard enthalpy change for the reaction CaCO3[s] CaO[s] + CO2[g] is 178.1 kJ. Use Table 5.3 to calculate
the standard enthalpy of formation of CaCO3[s].
Solution
Analyze Our goal is to obtain [CaCO3].
Plan We begin by writing the expression for the standard enthalpy change for the reaction:
= [CaO] + [CO2] – [CaCO3]
Solve
Inserting the given and the known values from Table 5.3 or Appendix C, we have:
178.1 kJ = –635.5 kJ – 393.5 kJ – [CaCO3]
Thermochemistry

Sample Exercise 5.12 Calculating an Enthalpy of Formation Using
an Enthalpy of Reaction
Continued
Solving for [CaCO3] gives:
[CaCO3] = –1207.1 kJ/mol
Check We expect the enthalpy of formation of a stable solid such as calcium carbonate to be negative, as obtained.
Practice Exercise 1
Given 2 SO2(g) + O2(g) 2 SO3(g), which of the following equations is correct?
(a) [SO3] = – [SO2]

(b) [SO3] = + [SO2]
(c) 2 [SO3] = +2 [SO2]
(d) 2 [SO3] = –2 [SO2]
(e) 2 [SO3] = 2 [SO2] –
Practice Exercise 2
Given the following standard enthalpy change, use the standard enthalpies of formation in Table 5.3 to calculate the
standard enthalpy of formation of CuO(s):
Thermochemistry
CuO(s) + H2(g) Cu(s) + H2O(l) H° = –129.7 kJ

Bond Enthalpy
• Bond Enthalpy - The enthalpy associated with
breaking one mole of a particular bond in a
gaseous substance.
Thermochemistry

Bond Enthalpy
• The bond enthalpy is always positive because energy is
required to break chemical bonds. Endothermic!
• Energy is always released when a bond forms between
gaseous fragments.
• The greater the bond enthalpy, the stronger the bond.
Thermochemistry

Bond Enthalpies and
• ADD bond energy for ALL bonds made (+)

• SUBTRACT bond energy for ALL bonds broken
(–)
• The result is an estimate of ΔH.
ΔHrxn = Σ (bond enthalpies – Σ (bond enthalpies

of bonds broken) of bonds formed)
Thermochemistry

Bond Enthalpies and
• So, we can predict
whether a
chemical reaction
will be
endothermic or
exothermic using
bond energies.
Thermochemistry

Sample Exercise 5.13 Estimating Reaction Enthalpies from Bond
Enthalpies
Use Table 5.4 to estimate H for the following combustion reaction.
ΔHrxn = Σ (bond enthalpies – Σ (bond enthalpies

of bonds broken) of bonds formed)
Solution
Analyze We are asked to use average bond enthalpies to estimate agreement is good. the enthalpy change for a
chemical reaction.
Plan Energy is required to break twelve C—H bonds and two C—C bonds in the two molecules of C 2H6, and seven
O O bonds in the seven O2 molecules. Energy is released by forming eight C O bonds, two per molecule of
CO2, and twelve O—H bonds, two per H2O molecule.
Thermochemistry

Sample Exercise 5.13 Estimating Reaction Enthalpies from Bond
Enthalpies
Continued
Solve Using Equation 5.32 and data from Table 5.4, we have
Check This estimate can be compared with the value of –2856 kJ calculated from more accurate thermochemical data;
the agreement is good.
Practice Exercise 1
Use the average bond enthalpies in Table 5.4 to estimate H for the “water splitting reaction”: H2O(g) H2(g)
+ ½ O2(g). (a) 242 kJ (b) 417 kJ (c) 5 kJ (d) –5 kJ (e) –468 kJ
Thermochemistry

Energy in Foods
• The energy released when one gram of food is
combusted is its fuel value.
Thermochemistry

Energy in Foods
• Most of the energy in foods comes from carbohydrates,
fats, and proteins.
• Carbohydrates (17 kJ/g):
C6H12O6(s) + 6 O2(g) 6 CO2(g) + 6 H2O(l) ΔH° = –2803 kJ
• Fats (38 kJ/g): Glyceryl tristearate, a solid saturated fat

2 C57H110O6(s) + 163 O2(g) 114 CO2(g) + 110 H2O(l) ΔH° = - 275,520 kJ
• Proteins produce 17 kJ/g (same as carbohydrates): Their

chemical reaction in the body is NOT the same as in a
calorimeter.
Thermochemistry

Energy in Fuels
The vast majority of the

energy consumed in
this country comes from
fossil fuels.
Thermochemistry

Other Energy Sources
• Nuclear fission
produces 8.6% of the
U.S. energy needs.
• Renewable energy
sources, like solar,
wind, geothermal,
hydroelectric, and
biomass sources
produce 9.9% of the
U.S. energy needs.
Thermochemistry

Sample Exercise 5.14 Estimating the Fuel Value of a Food from Its
Composition
(a) A 28-g (1-oz) serving of a popular breakfast cereal served with 120 mL of skim milk provides 8 g protein, 26 g
carbohydrates, and 2 g fat. Using the average fuel values of these substances, estimate the fuel value (caloric content)
of this serving. (b) A person of average weight uses about 100 Cal/mi when running or jogging. How many servings of
this cereal provide the fuel value requirements to run 3 mi?
Solution
Analyze (a) The fuel value of the serving will be the sum of the fuel values of the protein, carbohydrates, and fat.
(b) Here we are faced with the reverse problem, calculating the quantity of food that provides a specific fuel value.
Plan (a) We are given the masses of the protein, carbohydrates, and fat contained in a serving. We can use the data in
Table 5.4 to convert these masses to their fuel values, which we can sum to get the total fuel value. (b) The problem
statement provides a conversion factor between Calories and miles. The answer to part (a) provides us with a
conversion factor between servings and Calories.
Solve
(a)
Thermochemistry

Sample Exercise 5.14 Estimating the Fuel Value of a Food from Its
Composition
Continued
This corresponds to 160 kcal:
Recall that the dietary Calorie is equivalent to 1 kcal. Thus, the serving provides 160 Cal.
(b) We can use these factors in a straightforward dimensional analysis to determine the number of servings needed,
rounded to the nearest whole number:
Practice Exercise 1
A stalk of celery has a caloric content (fuel value) of 9.0 kcal. If 1.0 kcal is provided by fat and there is very little
protein, estimate the number of grams of carbohydrate and fat in the celery. (a) 2 g carbohydrate and 0.1 g fat (b) 2 g
carbohydrate and 1 g fat (c) 1 g carbohydrate and 2 g fat (d) 32 g carbohydrate and 10 g fat
Thermochemistry

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Lecture Presentation

• From Chapter 1, energy is the ability to do work

© 2018 Pearson Education, Inc.

© 2018 Pearson Education, Inc.

© 2012 Pearson Education, Inc.

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• Q = electric charge Thermochemistry

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• The SI unit of energy is the joule (J):

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© 2018 Pearson Education, Inc.

• The portion of the

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© 2018 Pearson Education, Inc.

© 2018 Pearson Education, Inc.

• Energy can be converted from one type to

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• As she coasts down the hill, her potential

© 2018 Pearson Education, Inc.

© 2018 Pearson Education, Inc.

© 2018 Pearson Education, Inc.

© 2018 Pearson Education, Inc.

© 2018 Pearson Education, Inc.

© 2018 Pearson Education, Inc.

© 2018 Pearson Education, Inc.

© 2018 Pearson Education, Inc.

© 2018 Pearson Education, Inc.

© 2018 Pearson Education, Inc.

© 2018 Pearson Education, Inc.

• However, q and w are

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Both path and state functions are often encountered in thermodynamics.

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© 2018 Pearson Education, Inc.

Solve The volume change is

V = Vfinal – Vinitial = 0.980 L – 0.250 L = 0.730 L

Thus, the quantity of work is

w = –PV = –(1.35 atm)(0.730 L) = –0.9855 L-atm

Converting L-atm to J, we have

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© 2018 Pearson Education, Inc.

• Enthalpy (H) is defined as the internal energy

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© 2018 Pearson Education, Inc.

© 2018 Pearson Education, Inc.

© 2018 Pearson Education, Inc.

• Usually the only

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© 2018 Pearson Education, Inc.

ΔHrxn = Hproducts − Hreactants

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1. Enthalpy is an extensive property: Therefore,

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© 2018 Pearson Education, Inc.

By adding the atomic weights of C and 4 H, we have

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• Since we cannot know the

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© 2018 Pearson Education, Inc.

Specific heat, then, is

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Using Equation 5.21, we have:

1 mol H2O = 18.0 g H2O