Chapter 6 Chemical Energy

Chapter 6
Chemical Energy
Prepared by:
Mark Emile H. Punzalan, B.S.Ch.E.
Department of Chemical Engineering
Faculty of Engineering
University of Santo Tomas
España, Manila, Philippines 1015
Energy
•  Usually defined as the capacity to do work1 or
produce heat2
•  The total energy of the universe is constant2
•  Energy can be classified as2:
–  PotenMal Energy
•  Energy due to posiMon or composiMon
–  KineMc energy
•  Energy due to the moMon of the object
1Chang, R. (2010). Chemistry (10th ed.). New York, NY: Mc-‐Graw Hill.
2Zumdahl, S. S. & Zumdahl, S. A. (2012). Chemistry: An Atoms First Approach. United States of America: Brooks/Cole, Cengage Learning
Chapter 6
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Chemical Energy
Thermochemistry
•  Thermochemistry is an aspect of
thermodynamics where rela.onship between
chemical reac.ons and energy changes is
examined1
•  It is the study of heat change in chemical
reacMons2
1Brown, T.L., LeMay, H.E., & Bursten, B.E. (1997). Chemistry: The Central Science (7th ed.) USA: PrenMce Hall InternaMonal
Chapter 6
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Chemical Energy
Units of Energy
•  The SI unit for energy is joule
•  A mass of 2 kg moving at speed of 1 m/s
possesses a kineMc energy of 1 J:
in honor of James Joule, a
1 2 BriMsh scienMst who
Ek = mv invesMgated work and heat
2
2
1 ! m$ kg ⋅m 2
Ek = (2kg) #1 & 1 2 = 1J
2 " s% s
Ref.: Brown, T.L., LeMay, H.E., & Bursten, B.E. (1997). Chemistry: The Central Science (7th ed.) USA: PrenMce Hall InternaMonal
Chapter 6
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Chemical Energy
Units of Energy
•  A calorie (cal) was defined as the amount of
energy required to raise the temperature of
1g of water from 14.5°C to 15.5°C.
1 cal = 4.184 J (exactly)
Chapter 6
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Chemical Energy
System and Surroundings
•  System is the part of the universe on which
we want to focus ahenMon to.
•  Surroundings includes everything else in the
universe

CH4 (g) + 2O2 (g) → CO2 (g) + 2H2O (g) + energy (heat)
Ref.: Zumdahl, S. S. & Zumdahl, S. A. (2012). Chemistry: An Atoms First Approach. United States of America: Brooks/Cole, Cengage Learning
Chapter 6
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Chemical Energy
System and Surroundings
•  Three types of systems
Open System Closed System Isolated System
Source: Chang, R. (2010). Chemistry (10th ed.). New York, NY: Mc-‐Graw Hill.
Chapter 6
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Chemical Energy
Exothermic and Endothermic
Process
Exothermic process. Any process that gives off
heat and transfers the thermal energy into the
surroundings.
2H2 (g) + O2 (g) → 2H2O (l) + energy (heat)

Endothermic process. Heat has to be supplied
to the system by the surroundings.
energy + 2HgO (s) → 2Hg (l) + O2 (g)
Ref.: Chang, R. (2010). Chemistry (10th ed.). New York, NY: Mc-‐Graw Hill.
Chapter 6
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Chemical Energy
Concept Check
Classify each process as exothermic or
endothermic. Explain. The system is underlined
in each example.
Exo a)  Your hand gets cold when you touch ice.
Endo b)  The ice gets warmer when you touch it.
Endo
c)  Water boils in a kehle being heated on a
stove.
Exo d)  Water vapor condenses on a cold pipe.
Endo e)  Ice cream melts.
Chapter 6
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Chemical Energy
The First Law of
Thermodynamics
•  Based on the law of conserva.on of energy
•  It states that energy can be converted from
one form to another, but cannot be created
nor destroyed
Chapter 6
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Chemical Energy
Internal Energy
•  The internal energy of the system most
precisely as the sum of the kine.c and
poten.al energies of all the “parMcles” in the
system ΔE = E final − Einitial
ΔE = q + w change in the internal
energy is always
measured
q represents heat
w represents work

Chapter 6
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Chemical Energy
11
Internal Energy
Ref.: Silberberg, M. S. (2007). Principles of General Chemistry (2nd ed.). New York, NY: Mc-‐Graw Hill
Chapter 6
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Chemical Energy
Sign conventions for WORK and
HEAT
Process Sign
Work done by the system on the
surroundings -‐

Work done on the system by the

surroundings +

Heat absorbed by the system from the

surroundings (endothermic process) +

Heat absorbed by the surroundings from the

-‐
system (exothermic process)
Chapter 6
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Chemical Energy
Relationship among q, w, and ΔE
Sign of ΔE = q + w
q > 0 and w > 0: ΔE > 0
q > 0 and w < 0: The sign of ΔE depends om the
magnitudes of q and w
q < 0 and w > 0: The sign of ΔE depends om the
magnitudes of q and w
q < 0 and w < 0: ΔE < 0
Chapter 6
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Chemical Energy
Internal Energy
Sample Problem The hydrogen and oxygen gases in the cylinder are ignited.
As the reacMon occurs, the system loses 1150 J of heat to
the surroundings. The reacMon also causes the piston to rise
as the hot gases expand. The expanding gas does 480 J of
work on the surroundings as it pushes against the
atmosphere. What is the change in the internal energy of
the system? Calculate in terms of J and calorie
SOLUTION:
q = -‐1150 J ΔE = q + w ΔE = ("1150&J) + ("480&J)
w = -‐480 J ΔE = !1630&J
ConverMng ΔE from J to cal:
1'cal
ΔE = "1630'J× = !389.58'cal
4.184'J
Chapter 6
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Chemical Energy
Internal Energy
Recall that: ΔE = q + w w = −PΔV
PV work
work done by the
expanding gas
SubsMtuMng work in the original equaMon: ΔE = qP − PΔV
heat at constant

Re-‐wriMng the equaMon in terms of qp: pressure
q p = ΔE + PΔV
Chang, R. (2010). Chemistry (10th ed.). New York, NY: Mc-‐Graw Hill.
Zumdahl, S. S. & Zumdahl, S. A. (2012). Chemistry: An Atoms First Approach. United States of America: Brooks/Cole, Cengage Learning

Chapter 6
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Chemical Energy
Enthalpy
Enthalpy of the system is defined as:
H = E + PV
Change in enthalpy is ΔH = ΔE + Δ ( PV )
But for a constant pressure process:
ΔH = ΔE + PΔV

Chapter 6
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Chemical Energy
Enthalpy
At constant
Recall that: q p = ΔE + PΔV pressure process:
and ΔH = ΔE + PΔV q p = ΔH
Therefore,
At constant pressure (where only PV work is allowed),
the change in enthalpy, ΔH, of the system is equal to
the energy flow as heat.

Chapter 6
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Chemical Energy
Enthalpy of Reaction
Enthalpy of reacMon is the difference between
the enthalpies of the products and enthalpies of
reactants:
ΔH = ΔH (products) – ΔH (reactants)

For endothermic process: ΔH > 0
For exothermic process: ΔH < 0


11/6/14
Chapter 6
Chemical Energy
19
Enthalpy of Reaction
Sample Problem Given the thermochemical equaMon
2SO2 (g) + O2 (g) → 2SO3 (g) ΔH = -‐198.2 kJ/mol
calculate the heat evolved when 87.9 g SO2 (molar mass = 64.07 g/mol) is
converted to SO3.
note that the
SOLUTION: enthalpy is
expressed in moles
1&mol&SO2 !198.2'kJ
ΔH = 87.9&g&SO2 × ×
64.07&g&SO2 2'mol'SO2
grams SO2 to moles SO2 conversion from
moles to kJ of
heat generated
ΔH = !136%kJ
Chapter 6
11/6/14 20
Chemical Energy
Standard Enthalpy of Reaction
•  The standard enthalpy of reacMon, ΔH°rxn, is
defined as the enthalpy of reacMon carried out
at 1 atm.

In an equaMon,
aA + bB → cC + dD

ΔH °
rxn = #cΔH f (C) + dΔH f ( D)% − #aΔH f ( A ) + bΔH f ( B)$%
" ° ° $ " ° °
° ° °
ΔH rxn = ΣnΔH ( products) − ΣmΔH ( reactants)
f f
Chapter 6
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Chemical Energy
Chapter 6
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Chemical Energy
Calculating the Heat of Reaction
from Heats of Formation
Sample Problem Nitric acid, whose worldwide annual producMon is
nearly 10 billion kilograms, is used to make many
products, including ferMlizers, dyes, and
explosives. The first step in the producMon
process is the oxidaMon of ammonia:
4NH3 (g) + 5O2 (g) → 4NO (g) + 6H2O (g)

Calculate the ΔH°rxn from ΔH°f values.
°
ΔH rxn = ΣnΔH f° ( products) − ΣmΔH f° ( reactants)
Chapter 6
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Chemical Energy
Nitric acid, whose worldwide annual producMon is nearly 10 billion
Sample Problem
kilograms, is used to make many products, including ferMlizers,
dyes, and explosives. The first step in the producMon process is the
oxidaMon of ammonia:
4 NH3 (g) + 5 O2 (g) → 4 NO (g) + 6 H2O (g)
SOLUTION:
°
ΔH rxn = ΣnΔH f° ( products) − ΣmΔH f° ( reactants)
= {4ΔH f° "#NO ( g)$% + 6ΔH f° "#H 2 O ( g)$%} − {4ΔH f° "#NH 3 ( g)$% +
5ΔH f° "#O 2 ( g)$%}

products
Ref.: Silberberg, M. S. (2007). Principles of General Chemistry (2nd ed.). New York, NY: Mc-‐Graw Hill reactants
Chapter 6
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Chemical Energy
Nitric acid, whose worldwide annual producMon is nearly 10 billion
Sample Problem
kilograms, is used to make many products, including ferMlizers,
dyes, and explosives. The first step in the producMon process is the
oxidaMon of ammonia:
4 NH3 (g) + 5 O2 (g) → 4 NO (g) + 6 H2O (g)
SOLUTION:
ΔH°f (NO) ΔH°f (H2O)
! n NO
kJ $ ! kJ $ n H2O
°
ΔH rxn = ( 4 mol) # 90.3 & + ( 6 mol) # -241.8 &
" mol % " mol %
( " kJ % " kJ %+
−*( 4 mol) $ −45.9 ' + ( 5 mol) $ 0 '-
) # mol & n O2 # mol &,
° n NH3 ΔH°f (NH3) ΔH°f (O2)
ΔH rxn = -906 kJ
Chapter 6
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Chemical Energy
Hess’s Law
“In going from a parOcular set of reactants to a
parOcular set of products, the change in
enthalpy is the same whether the reacOon takes
place in one step or in a series of steps”1

“The enthalpy change of an overall process is
the sum of the enthalpy changes of its
individual steps.”2

2Silberberg, M. S. (2007). Principles of General Chemistry (2nd ed.). New York, NY: Mc-‐Graw Hill
Chapter 6
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Chemical Energy
Hess’s Law
N2 (g) + 2O2 (g) → 2NO2 (g) ΔH1 = 68 kJ
•  This reacMon also can be carried out in two disMnct
steps, with enthalpy changes designated by ΔH2 and
ΔH3.
N2 (g) + O2 (g) → 2NO (g) ΔH2 = 180 kJ

2NO (g) + O2 (g) → 2NO2 (g) ΔH3 = – 112 kJ
N2 (g) + 2O2 (g) → 2NO2(g) ΔH2 + ΔH3 = 68 kJ

ΔH1 = ΔH2 + ΔH3 = 68 kJ
Chapter 6
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Chemical Energy
Hess’s Law
Chapter 6
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Chemical Energy
Characteristicas of Enthalpy
Changes in a Reaction
•  If a reac.on is reversed, the sign of ΔH is
also reversed.
•  The magnitude of ΔH is directly proporMonal
to the quanMMes of reactants and products in
a reacMon. If the coefficients in a balanced
reacMon are mul.plied by an integer, the
value of ΔH is mul.plied by the same
integer.
Chapter 6
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Chemical Energy
Hess’s Law
Sample Problem Two gaseous pollutants that form in auto exhaust
are CO and NO. An environmental chemist is
studying ways to convert them to less harmful
gases through the following equaMon:
1
CO(g)$$ +$$$NO(g)$$ → CO2 $(g) $+$$ N2 $ (g) ΔH = ?
2
Given the following informaMon, calculate the unknown ΔH:
1
EquaMon A: CO# (g)$ +# O2 # (g)→ CO2 (g)
ΔHA = #283.0)kJ
2
EquaMon B: N2 # (g)$ +##O2 # (g)→ 2NO (g)
ΔHB = 180.6(kJ
Chapter 6
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Chemical Energy
Hess’s Law target equaKon
1
Sample Problem CO
(g)$$ +$$$NO(g)$$ → CO2 $(g) $+$$ N2 $ (g) ΔH = ?
2
1
EquaMon A: CO# (g)$ +# O2 # (g)→ CO2 (g) ΔHA = #283.0)kJ
2
EquaMon B: N2 # (g)$ +##O2 # (g)→ 2NO (g)
ΔHB = 180.6(kJ
Sign of
Reversing equaMon B to saMsfy the target equaMon: enthalpy was
also reversed
EquaMon B (reversed):
2NO(g) → N2 $ (g)$ +$$O2 $ (g) ΔHB = #180.6)kJ
Chapter 6
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Chemical Energy
Hess’s Law
target equaKon
1
Sample Problem
CO(g)$$ +$$$NO(g)$$ → CO2 $(g) $+$$ N2 $ (g) ΔH = ?
2
EquaMon B (reversed):
2NO(g) → N2 $ (g)$ +$$O2 $ (g) ΔHB = #180.6)kJ

Note that there is 1 mol of NO in the Also, there is 0.5 mol of nitrogen in the
target equaKon and 2 moles of NO in target equaKon while 1 mol of
EquaKon B nitrogen is required in EquaKon B
Divide by 2 the reversed equaMon B to saMsfy the number of moles
Enthalpy
in the target equaMon: should also be
Corrected moles of EquaMon B (reversed): divided by two
1 1 ΔHB = #90.3(kJ
NO(g)$$ → O2 $(g) $+&& N2 & (g)
2 2
Chapter 6
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Chemical Energy
Hess’s Law
target equaKon
1
Sample Problem
CO(g)$$ +$$$NO(g)$$ → CO2 $(g) $+$$ N2 $ (g) ΔH = ?
2
Solving for ΔH (by adding the two equaMon):
EquaMon B 1 1
(reversed and divided by 2): NO(g)$$ → O2 $(g) $+&& N2 & (g) ΔHB = #90.3(kJ
2 2
1
EquaMon A: CO# (g)$ +# O2 # (g)→ CO2 (g) ΔHA = #283.0)kJ
2
1
CO(g)$$ +$$$NO(g)$$ → CO2 $(g) $+$$ N2 $ (g)
2
ΔH = ΔHA + ΔHB = -‐ 373.3 kJ
Chapter 6
11/6/14 33
Chemical Energy

Chapter 6 Chemical Energy

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Chapter 6 Chemical Energy

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Chapter 6

1 cal = 4.184 J (exactly)

Open System Closed System Isolated System

Work done on the system by the

Heat absorbed by the system from the

Heat absorbed by the surroundings from the

SubsMtuMng work in the original equaMon: ΔE = qP − PΔV

heat at constant

4NH3 (g) + 5O2 (g) → 4NO (g) + 6H2O (g)

5ΔH f° "#O 2 ( g)$%}

N2 (g) + O2 (g) → 2NO (g) ΔH2 = 180 kJ

2NO(g) → N2 $ (g)$ +$$O2 $ (g) ΔHB = #180.6)kJ

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