Energy and Chemical Change

Chapter 6
Basic Chemistry (CH1101)
2017-2018
References:
Brady, J, E., Jepersen, N. D., Hyslop A., 2012, Chemistry, 7th Edition, International Student Version, John
Wiley and Sons.
Raymond Chang and Kenneth A. Goldsby, 2012, Chemistry, McGraw-Hill
Outline
1. Energy
2. Learn and apply the first law of thermodynamics :
heat, internal energy, and work
3. Determine the amount of heat exchanged by
Calorimetry
4. Enthalpy of chemical reaction
5. Explore the utility of and assumptions in
thermochemical equations
6. Standard enthalpy of formation and reaction
7. Uses Hess’s Law to predict enthalpies reaction
1. Energy
Energy is the capacity to do work
•R adiant energy comes from the sun
and is earth’s primary energy source
•Therm al energy is the energy
associated with the random motion of
atoms and molecules
•Nuclear energy is the energy stored
within the collection of neutrons and
protons in the atom
•Chem ical energy is the energy stored
within the bonds of chemical substances
•P otential energy is the energy
available by virtue of an object’s position
 Energy Changes in Chemical
Reactions
Heat is the transfer of thermal energy between two
bodies that are at different temperatures.
Temperature is a measure of the thermal energy.
Temperature = Thermal Energy

400C
400C
greater thermal energy
 Thermochemistry
• Study of energies given off by or absorbed by
reactions
Thermodynamics
• the scientific study of the interconversion of
heat and other kinds of energy.
Energy (E )
• Ability to do work or to transfer heat

Kinetic Energy (KE) Potential Energy (PE)

• Energy of motion • Stored Energy (Stored in Chemical
• KE = ½m v 2 Bonds  Chemical Energy)
• Springs • Exists in natural attractions
and repulsions
Law of Conservation of Energy
• Energy can neither be created nor destroyed
• Can only be converted from one form to another
• Total energy of universe is constant
Total Energy = Potential Energy + Kinetic Energy
Units of Energy
Joule (J)
• Kinetic Energy possessed by 2 kg object moving at speed of
1 m/s. 1 1 m 
2

1 J = (2 kg) 
2  1 s 
• If calculated value is greater than 1000 J, use kilojoules (kJ)
A calorie (cal)
• Energy needed to raise the temperature of 1 g H2O by 1 °C
• 1 cal = 4.184 J (exactly)
Your Turn!
Which of the following is not a form of kinetic energy?

A. A pencil rolls across a desk

B. A pencil is sharpened
C. A pencil is heated
D. A pencil rests on a desk
E. A pencil falls to the floor
Your Turn!
Which of the following represents an increase in the
potential energy of the system?

A. Na  Na+ + e–
B. A periodic table falls off the wall
C. Ca2+ + 2e–  Ca
D. A firecracker explodes
E. Gasoline is burned and creates CO2 and H2O
Temperature vs. Heat
Temperature hot cold
• Proportional to average kinetic energy of
object’s particles
• Higher average kinetic energy means :
Higher temperature and Faster moving
molecules
Heat
• Total amount of energy transferred between
objects
• Heat transfer is caused by a temperature
difference
• Always passes spontaneously from warmer
objects to colder objects
• Transfers until both are the same temperature
(Thermal Equilibrium)
• Energy transferred through heat comes from internal energy
Defining the System
System
• What we are interested in studying
• Reaction in beaker
Surroundings
• Everything else
• Room in which reaction is run
Boundary
• Separation between system and surroundings
• Visible Example: Walls of beaker
• Invisible Example: Line separating warm and cold
fronts
System
The system is the specific part of the universe
that is of interest in the study.

open closed isolated

Exchange: mass & energy energy nothing

Adiabatic Process : Process that occurs in

isolated system
Chemical Reactions
Forming Bonds
• Atoms that are attracted to each other are moved
closer together
• Decrease the potential energy of reacting system
• Releases energy

Breaking Bonds
• Atoms that are attracted to each other are forced
apart
• Increase the potential energy of reacting system
• Requires energy
Chemical Reactions Process
Ex otherm ic process is any process that gives off heat
– transfers thermal energy from the system to the
surroundings.
2H2 (g) + O2 (g) 2H2O (l) + energy

H2O (g) H2O (l) + energy

Endotherm ic process is any process in which heat

has to be supplied to the system from the surroundings.

energy + 2HgO (s) 2Hg (l) + O2 (g)

energy + H2O (s) H2O (l)

Thermodynamics
Thermodynamics is the scientific study of the
interconversion of heat and other kinds of energy.

State functions are properties that are determined by the

state of the system, regardless of how that condition
was achieved.
energy, pressure, volume, temperature
∆E = Efinal - Einitial
∆P = Pfinal - Pinitial

∆V = Vfinal - Vinitial
∆T = Tfinal - Tinitial
Potential energy of hiker 1 and hiker 2
is the same even though they took
different paths.
2.The First Law of Thermodynamics
First law of thermodynamics – energy can
be converted from one form to another,
but cannot be created or destroyed.
∆Esystem + ∆Esurroundings = 0
or
∆Esystem = -∆Esurroundings
C3H8 + 5O2 3CO2 + 4H2O

Exothermic chemical reaction!

Chemical energy lost by combustion = Energy gained by the surroundings

system surroundings
Another form of the first law for
∆Esystem
∆E = q + w
∆E is the change in internal energy of a system
q is the heat exchange between the system and the surroundings
w is the work done on (or by) the system
w = -P∆V when a gas expands against a constant external
pressure
q is (+) Heat absorbed by system (IN)
q is (–) Heat released by system (OUT)
w is (+) Work done on system (IN)
w is (–) Work done by system (OUT)
Endothermic reaction : ∆E = +
Exothermic reaction : ∆E = –
∆E, Change in Internal Energy
• For reaction: reactants → products
• ∆E = E products – E reactants
• Can use to do something useful
• Work
• Heat
• If system absorbs energy during reaction
• Energy coming into system has a positive sign (+)
• Final energy > initial energy
Example: Photosynthesis or charging battery
• As system absorbs energy
• Increase potential energy
• Available for later use
Your Turn!

A gas releases 3.0 J of heat and then performs 12.2 J

of work. What is the change in internal energy of the
gas?
A. –15.2 J
B. 15.2 J ∆E = q + w
C. –9.2 J
∆E = – 3.0 J + (–12.2 J)
D. 9.2 J
E. 3.0 J
Work Done On the System
w=Fxd
w = -P ∆V ∆V > 0
-P∆V < 0
P x V = F x d3 = F x d = w wsys < 0
d2

Work is not
a state
function!

∆w = wfinal - winitial initial final

Your Turn!
A sample of nitrogen gas expands in volume from 1.6 L to
5.4 L at constant temperature. What is the work done in
joules if the gas expands (a) against a vacuum and (b)
against a constant pressure of 3.7 atm?
w = -P ∆V
(a) ∆V = 5.4 L – 1.6 L = 3.8 L P = 0 atm
W = -0 atm x 3.8 L = 0 L•atm = 0 joules

(b) ∆V = 5.4 L – 1.6 L = 3.8 L P = 3.7 atm

w = -3.7 atm x 3.8 L = -14.1 L•atm

w = -14.1 L•atm x101.3 J = -1430 J
1L•atm
 Your Turn!
A reaction contracts by 1.534 L under a constant
pressure of 2.134 atm while releasing 200.7 J of heat to
the surrounding. What is the change in internal energy
of the system? 1.000 Latm = 101.3 J
A. 131.0 J E = q + w = -200.7 J + w
B. 532.4 J Work = –P ×∆V
= -2.134 atm × 1.534 L = 3.274 Latm
C. -131.0 J
D. -532.4 J 101.3 J
= 3.274 Latm × = 331.7 J
E. 331.6 J 1.000 Latm
E = q + w = -200.7 J + 331.7
= 131.0 J
21
Heat (q )
• Heat is the energy transferred between two objects
• Cannot measure heat directly
• Heat (q ) gained or lost by an object
• Directly proportional to temperature change (∆T) it
undergoes
• Adding heat, increases temperature
• Removing heat, decreases temperature
• Measure changes in temperature to quantify amount
of heat transferred
q = C × ∆T
• C = heat capacity
Direction of Heat Flow
• Heat lost by one object has the same
magnitude as heat gained by other object
• Sign of q indicates direction of heat flow
• Heat is gained, q is positive (+)
• Heat is lost, q is negative (–)
q 1 = –q 2
Example: A piece of warm iron is placed into
beaker of cool water. Iron loses 10.0 J of
heat, water gains 10.0 J of heat
qiron = –10.0 J qwater = +10.0 J
Heat Capacity (C )
• Amount of heat (q ) required to raise
temperature of object by 1 °C
Heat Exchanged = Heat Capacity × ∆T
q = C × ∆T
• Units for C = J/°C or J⋅°C –1
• Extensive property
• Depends on two factors
1. Sample size or amount (mass)
• Doubling amount doubles heat capacity
2. Identity of substance
• Water vs. iron
Learning Check: Heat Capacity
A cup of water is used in an experiment. Its heat
capacity is known to be 720 J/˚C. How much heat
will it absorb if the experimental temperature
changed from 19.2 ˚C to 23.5 ˚C?

q = C × ∆T

q = 3.1 × 103 J
25
Your Turn!

Which of the following is not an expression for

the First Law of Thermodynamics?
A. Energy is conserved
B. Energy is neither created nor destroyed
C. The energy of the universe is constant
D. Energy can be converted from work to heat
E. The energy of the universe is increasing
Your Turn!
A ball bearing at 260.0 ˚C is dropped into a cup
containing 250. g of water. The water warms
from 25.0 to 37.3 ˚C. What is the heat capacity
of the ball bearing in J/˚C?
Heat capacity of the cup of water = 1046 J / ˚C
qlost by ball bearing = –qgained by water
1. Determine temperature change of water 4. Determine T change of ball bearing
∆T water = (37.3 ˚ C – 25.0 ˚C) = 12.3 ˚C
∆T ball bearing = (37.3 ˚C – 260.0 ˚C)
2. Determine how much heat gained by water
= –222.7 ˚ C
qwater = Cwater × ∆Twater = 1046 J/˚C × 12.3 ˚C
5. Calculate C of ball bearing
= 12.87 ×103 J q – 12.87 × 103 J
3. Determine how much heat ball bearing lost C= = = 57.8 J/˚ C
∆T − 222.7 °C
qball bearing = – qwater = –12.87 × 103 J
Specific Heat (s )
• Amount of heat energy needed to raise
temperature of 1 g substance by 1 °C
C=s×m or
• Intensive property
• Ratio of two extensive properties
• Units
• J/(g °C) or J g−1 °C−1
• Unique to each substance
• Large specific heat means substance releases
large amount of heat as it cools
Specific Heats of Some
Substances
Using Specific Heat

Heat Exchanged = (Specific Heat × mass) × ∆T

q = s × m × ∆T
Units = J/(g °C) × g × °C = J
• Substances with high specific heats resist changes in
temperature when heat is applied
• Water has unusually high specific heat
• Important to body (~60% water)
• Used to cushion temperature changes
• Why coastal temperatures are different from inland
temperatures
Your Turn!
How much heat energy must you lose from a 250.
mL cup of coffee for the temperature to fall from
65.0 ˚C to 37.0 ˚C? (Assume density of coffee =
1.00 g/mL, s coffee = s water = 4.18 J/g˚C)

q = s × m × ∆T
∆T = 37.0 – 65.0 ˚ C = – 28.0 ˚C
q = 4.18 J/g˚C × 250. mL × 1.00 g/mL × (– 28.0 ˚C)
q = (–29.3 × 103 J) = –29.3 kJ
Your Turn!
If a 38.6 g piece of gold absorbs 297 J of heat, what
will the final temperature of the gold be if the initial
temperature is 24.5 ˚C? The specific heat of gold is
0.129 J/g˚C.
Need to find tfinal ∆T = T f – T i
First use q = s × m × ∆T to calculate ∆T
q 297 J
∆T = = = 59.6 ˚ C
s×m 0.129 J/g C × 38.6 g
Next calculate Tfinal
59.6 °C = Tf – 24.5 °C
Tf = 59.6 °C + 24.5 °C = 84.1 °C
 To be continued…

References:
Brady, J, E., Jepersen, N. D., Hyslop A., 2012, Chemistry, 7th Edition, International Student Version, John
Wiley and Sons.
Raymond Chang and Kenneth A. Goldsby, 2012, Chemistry, McGraw-Hill
Outline
1. Energy
2. Learn and apply the first law of thermodynamics :
heat, internal energy, and work
3. Determine the amount of heat exchanged by
Calorimetry
4. Enthalpy of chemical reaction
5. Explore the utility of and assumptions in
thermochemical equations
6. Standard Enthalpy of Formation and Reaction
7. Uses Hess’s Law to predict enthalpies reaction
3. Determine the amount of heat
exchanged by Calorimeter
Calorimeter
• Instrument used to measure temperature
changes
• Container of known heat capacity
• Use results to calculate heat of reaction

• Two Types:
a. Constant pressure: a coffee cup calorimeter
b. Constant volume: a Bomb Calorimeter Heat
exhange depends on Temperature Change
Coffee Cup Calorimeter
(Constant P)
• Simple ; Measures q P
• Open to atmosphere, Let heat be
exchanged between reaction and
water, and measure change in
temperature
• Very little heat lost
• Calculate heat of reaction
qsys = qwater + qcal + qrxn
qsys = 0
qrxn = - (qwater + qcal) Reaction at Constant P
qwater = m x s x ∆Τ
∆H = qrxn
qcal = Ccal x ∆Τ
Bomb Calorimeter (Constant V )
• Vessel in center with rigid
walls
• No change in volume, so ∆V
= 0 so P∆V = 0
• Heavily insulated vat
• Water bath
• No heat escapes
• ∆E = q – P ∆V = q + 0 = q v
• ∆E = q + 0 = qv
• subscript ‘v’ emphasizes
qsys = q calorimeterbomb + qrxn constant volume
qsys = 0 Reaction at Constant V
qrxn = - (q cal bomb) ∆H = qrxn
qbomb = Cbomb x ∆Τ
Learning Check
When 1.000 g of olive oil is completely burned in pure
oxygen in a bomb calorimeter, the temperature of the
water bath increases from 22.000 ˚C to 26.049 ˚C.
How many Calories are in olive oil, per gram? The heat
capacity of the calorimeter is 9.032 kJ/˚C.
∆T = 26.049 ˚C – 22.000 ˚C = 4.049 ˚C
qabsorbed by calorimeter = C∆t = 9.032 kJ/°C × 4.049 ˚C
= 36.57 kJ
qreleased by oil = – qcalorimeter = – 36.57 kJ
− 36.57 kJ 1 kcal 1 Cal
q oil (in cal/g) = × ×
1.000 g 4.184 kJ 1 kcal
= –8.740 Cal/g oil
Your Turn!
A 43.29 g sample of solid is transferred from boiling
water (T = 99.8 ˚C) to 152 g water at 22.5 ˚C in a
coffee cup. The temperature of the water rose to 24.3
˚C. Calculate the specific heat of the solid. (q absorbed
by calorimeter is negligible)
q = m × s × ∆T
A. –1.1 × 103 J g–1 ˚C–1
B. 1.1 × 103 J g–1 ˚C–1
C. 1.0 J g–1 ˚C–1 = 1.1 × 103 J
D. 0.35 J g–1 ˚C–1 qsample = – qwater = – 1.1 × 103 J

E. 0.25 J g–1 ˚C–1 − 1.1 × 10 3 J

s =
43.29 g × (24.3 – 99.8)  C
Comparing q V and q P
• Difference between q V and q P can be significant
• Reactions involving large volume changes,
• Consumption or production of gas
• Consider gas phase reaction in cylinder immersed in
bucket of water
• Reaction vessel is cylinder topped by piston
• Piston can be locked in place with pin
• Cylinder immersed in insulated bucket containing weighed
amount of water
• Calorimeter consists of piston, cylinder, bucket, and water
Comparing q V and q P
 Heat capacity of calorimeter = 8.101 kJ/°C
 Reaction run twice, identical amounts of reactants
Run 1: qV - Constant Volume
 Same reaction run once at constant
volume and once at constant pressure
 Pin locked
 Ti = 24.00 °C; Tf = 28.91 °C
qCal = C∆T
= 8.101 J/°C × (28.91 – 24.00)°C = 39.8 kJ
qV = – qCal = –39.8 kJ
Comparing q V and q P
Run 2: q P
• Run at atmospheric pressure
• Pin unlocked
• Ti = 27.32 °C; Tf = 31.54 °C
• Heat absorbed by calorimeter is
q Cal = C ∆T
= 8.101 J/°C × (31.54 − 27.32)°C
= 34.2 kJ
q P = – q Cal = –34.2 kJ
Comparing q V and q P
• q V = -39.8 kJ
• q P = -34.2 kJ
• System (reacting mixture) expands, pushes against
atmosphere, does w ork
• Uses up some energy that would otherwise be heat
• Work = (–39.8 kJ) – (–34.2 kJ) = –5.6 kJ
• Expansion work or pressure volume work
• Minus sign means energy leaving system
4. Enthalpy (H ) of Chemical Reaction

• Heat of reaction at constant pressure (q P )

H = E + PV
• Similar to E, but for systems at constant P
• Now have P∆V work + heat transfer
• H = state function
• At constant pressure
∆ H = ∆ E + P ∆ V = (q P + w ) + P ∆ V
If only work is P–V work, w = – P ∆V
∆H = (q P + w ) – w = q P
Enthalpy Change (∆H )
H is a state function
• ∆H = H final – H initial
• ∆H = H products – H reactants
• Significance of sign of ∆H
Endothermic reaction
• System absorbs energy from surroundings
• ∆H positive
Exothermic reaction
• System loses energy to surroundings
• ∆H negative
Enthalpy Change (∆H )
∆H = H (products) – H (reactants)
∆H = heat given off or absorbed during a reaction at constant
pressure

Hproducts > Hreactants Hproducts < Hreactants

∆H > 0 ∆H < 0 6.4
∆H in Chemical Reactions

N2(g) + 3H2(g) → 2 NH3(g)

1.000 mol 3.000 mol 2.000 mol
• When 1 mol N2 and 3 mol H2 react to form 2 mol NH3
; 92.38 kJ released
Therefore ∆H°= –92.38 kJ
• Exothermic reaction!
5. Explore the utility of and assumptions in
thermochemical equations
Thermochemical Equations
 Write ∆H immediately after equation
N2(g ) + 3H2(g ) → 2NH3(g ) ∆H °= –92.38 kJ

• Must give physical states of products and reactants

(∆H different for different states  State Matters!)
CH4(g) + 2O2(g) → CO2(g) + 2H2O(l ) ∆H ° rxn = –890.5 kJ
CH4(g) + 2O2(g) → CO2(g) + 2H2O(g ) ∆H ° rxn = –802.3 kJ

Difference is equal to the energy to vaporize

water
Thermochemical Equations
• Example :
N2(g) + 3H2(g) → 2NH3(g) ∆H° = –92.38 kJ
• In Thermochemical Equation,
coefficients is the number of moles
• 92.38 kJ released when 2 moles of NH3 formed
• If 10 mole of NH3 formed
5N2(g) + 15H2(g) → 10NH3(g) ∆H°= –461.9 kJ
• ∆H = (5 × –92.38 kJ) = – 461.9 kJ
• Can have fractional coefficients
• Fraction of mole, NOT fraction of molecule
½N2(g) + 3/2H2(g) → NH3(g) ∆H° rxn = –46.19 kJ
Learning Check:
Consider the following reaction:
2C2H2(g) + 5O2(g) → 4CO2(g) + 2H2O(g)
ΔH° = –2511 kJ
The reactants (acetylene and oxygen) have 2511 kJ
more energy than products. How many kJ are
released for 1 mol C2H2?

–1,256 kJ
 Your Turn!
Rxn. 1: C3H8(g) + 5O2(g) → 3 CO2(g) + 4 H2O(g)
ΔH °rxn= –2043 kJ
Rxn. 2: C3H8(g) + 5O2(g) → 3 CO2(g) + 4 H2O(l )
ΔH °rxn = –2219 kJ
Why does rxn. 2 release more heat than rxn. 1?
A. It shouldn’t, and the DH values should be equal
B. More reactants must have been used in rxn. 2
C. In rxn. 1 some of the heat of the reaction is used up
converting liquid water to gas, so less heat can be given off.
D. Liquids always have lower temperatures than gases
Reversing Thermochemical
Equations
Consider
CH4(g) + 2O2(g) → CO2(g) + 2H2O(g)
∆H reaction = – 802.3 kJ
• Reverse thermochemical equation
• Must change sign of ∆H
CO2(g) + 2H2O(g) → CH4(g) + 2O2(g)
∆H reaction = 802.3 kJ

• Get energy out when form products

• Must put energy in to go back to reactants
 To be continued…

References:
Brady, J, E., Jepersen, N. D., Hyslop A., 2012, Chemistry, 7th Edition, International Student Version, John
Wiley and Sons.
Raymond Chang and Kenneth A. Goldsby, 2012, Chemistry, McGraw-Hill
Outline
1. Energy
2. Learn and apply the first law of thermodynamics :
heat, internal energy, and work
3. Determine the amount of heat exchanged by
Calorimetry
4. Enthalpy of chemical reaction
5. Explore the utility of and assumptions in
thermochemical equations
6. Standard Enthalpy of Formation and Reaction
7. Uses Hess’s Law to predict enthalpies reaction
6. Standard Enthalpy of Formation
and Reaction
Thermodynamic Quantities
• E and H are state functions and are also
extensive properties
• ∆EO and ∆Ho are measurable changes but still
extensive properties
• ∆H °f are standard entalphy of
formation and intensive properties
• Units of kJ /mol for formation reactions and phase
changes (e.g., ∆H °f or ∆H °vap)
• Units of kJ for balanced chemical equations
(∆H °reaction)
∆H ° in Chemical Reactions
A standard state specifies all the necessary parameters
to describe a system. Generally this includes the pressure,
temperature, and amount and state of the substances
involved
Standard Conditions for ∆H 's
• 1 atm (gas) or 1 M (aqueous)
Standard Heat of Reaction (∆H °)
• Enthalpy change for reaction at 1 atm
Example: N2(g) + 3H2(g) → 2 NH3(g)
1.000 mol 3.000 mol 2.000 mol
• When 1 mol N2 and 3 mol H2 react to form 2 mol NH3
usually data at 25 °C and 1 atm 92.38 kJ released
• ∆Ho= –92.38 kJ (exothermic reaction)
∆H ° in Chemical Reactions
Thermochemical Equations:
N2(g) + 3H2(g) → 2NH3(g) ∆Ho= –92.38 kJ

How if the reaction a half of aboved reaction?

½N2(g ) + 3/2H2(g ) → NH3(g ) ∆H °rxn = –46.19 kJ

• Calculate entalphy reaction from data of ∆Hof

∆Horxn = Σn ∆Hfo products - Σn ∆Hfo reactants

 Because there is no way to measure the absolute value of
the enthalpy of a substance, must I measure the enthalpy
change for every reaction of interest?
Establish an arbitrary scale with the standard enthalpy of
formation (∆H0) as a reference point for all enthalpy expressions.
f
Standard enthalpy of form ation (∆H0) is the heat change
f
that results when one mole of a compound is formed
from its elements at a pressure of 1 atm.
The standard enthalpy of formation of any element in its most
stable form is zero.
∆H0 (O2) = 0 ∆H0 (C, graphite) = 0
f f
∆H0 (O3) = 142 kJ/mol ∆H0 (C, diamond) = 1.90 kJ/mol
f f
Standard State
• Most stable form and physical state of element at
1 atm (1 bar) and 25 °C (298 K)
Element Standard
state Note: All ∆Hf° of elements in
O O2(g) their standard states = 0
C C (s, gr)
Forming element from itself.
H H2(g)
Al Al(s)
Ne Ne(g)
 See Appendix in back of textbook and Table 6.2
Type of ∆H ° reaction
Learning Check
Benzene (C6H6) burns in air to produce carbon dioxide and
liquid water. How much heat is released per mole of benzene
combusted? The standard enthalpy of formation of benzene
is 49.04 kJ/mol, carbon dioxide is -393.5 kJ/mol, and water is
-187.6 kJ/mol.
2C6H6 (l) + 15O2 (g) 12CO2 (g) + 6H2O (l)

∆Ho rxn = Σn ∆Hfoproducts - Σn ∆Hfo reactants

∆Hrxn = (12∆Hof(CO2)) + (6∆Hof(H2O)) - (2∆Hof(C6H6)) - (15∆Hof(O2))
= (12 x (-393.5)) + (6 x (-187.6)) – (2 x 49.04) – 0 kJ

= -5946 kJ (in 2 moles)

∆Horxn(C6H6) = ∆Ho rxn /n = (-5946 kJ)/ 2 mol = -2973 kJ/mol
Multiple Paths; Same ∆H °
• Can often get from reactants to products by
several different paths

Reactants Products

Intermediate A Intermediate B

 Should get same ∆H °

 Enthalpy is state function and path independent
 Let’s see if this is true
Multiple Paths; Same ∆H °
Path a: Single step
C(s) + O2(g) → CO2(g) ∆H°rxn = –393.5 kJ

Path b: Two step

Step 1: C(s) + ½O2(g) → CO(g) ∆H °rxn = –110.5 kJ
Step 2: CO(g) + ½O2(g) → CO2(g) ∆H °rxn = –283.0 kJ
Net Rxn: C(s) + O2(g) → CO2(g) ∆H °rxn = –393.5 kJ
• Chemically and thermochemically, identical results
• True for exothermic and endothermic reactions
7. Uses Hess’s Law to predict
enthalpies reaction
Hess’s Law of Heat Summation
• Going from reactants to products
• Enthalpy change is same whether reaction takes
place in one step or many
• Chief Use
• Calculation of ∆H °rxn for reaction that can’t be measured
directly
• Thermochemical equations for individual steps
of reaction sequence may be combined to obtain
thermochemical equation of overall reaction
Enthalpy Diagrams
• Graphical description of Hess’ Law
• Vertical axis = enthalpy scale
• Horizontal line =various states of reactions
• Higher up = larger enthalpy
• Lower down = smaller enthalpy

Hess’s Law of Heat Summation : For any reaction that can be written into steps,
value of ∆H °rxn for reactions = sum of ∆H °rxn values of each individual step
Rules for Manipulating
Thermochemical Equations

1. When equation is reversed, sign of ∆H°rxn must also

be reversed.
2. If all coefficients of equation are multiplied or
divided by same factor, value of ∆H°rxn must likewise
be multiplied or divided by that factor
3. Formulas canceled from both sides of equation must
be for substance in sam e physical states
Strategy for Adding Reactions
Together:
1. Choose most complex compound in equation for
one-step path
2. Choose equation in multi-step path that contains
that compound
3. Write equation down so that compound
• is on appropriate side of equation
• has appropriate coefficient for our reaction
4. Repeat steps 1 – 3 for next most complex
compound, etc.
Strategy for Adding Reactions (Cont.)
5. Choose equation that allows you to
• cancel intermediates
• multiply by appropriate coefficient
6. Add reactions together and cancel like terms
7. Add energies together, modifying enthalpy values
in same way equation modified
• If reversed equation, change sign on enthalpy
• If doubled equation, double energy
Calculate ∆H o
rxn for
C (s, graphite) → C (s, diamond)
Given C (s, gr) + O2(g) → CO2(g) ∆H°rxn = –394 kJ
–1×[C (s, dia) + O2(g) → CO2(g) ∆H°rxn = –396 kJ ]
• To get desired equation, must reverse second
equation and add resulting equations
C(s, gr) + O2(g) → CO2(g) ∆H°rxn = –394 kJ
CO2(g) → C(s, dia) + O2(g) ∆H°rxn = –(–396 kJ)
C(s, gr) + O2(g) + CO2(g) → C(s, dia) + O2(g) + CO2(g)

∆H° = –394 kJ + 396 kJ = + 2 kJ

 Your Turn!

Which of the following is a statement of Hess's Law?

A. ∆H for a reaction in the forward direction is equal to ∆H
for the reaction in the reverse direction.
B. ∆H for a reaction depends on the physical states of the
reactants and products.
C. If a reaction takes place in steps, ∆H for the reaction
will be the sum of ∆Hs for the individual steps.
D. If you multiply a reaction by a number, you multiply ∆H
by the same number.
E. ∆H for a reaction in the forward direction is equal in
magnitude and opposite in sign to ∆H for the reaction in
the reverse direction.
Your Turn!
Given the following data:
C2H2(g) + 5/2O2(g) → 2CO2(g) + H2O(l ) ∆H rxn= –1300.
kJ
C(s) + O2(g) → CO2(g) ∆Hrxn = –394 kJ
H2(g) + 1/2O2(g) → H2O(l ) ∆Hrxn = –286 kJ
Calculate for the reaction
2C(s) + H2(g) → C2H2(g)
A. 226 kJ
B. –1980 kJ ∆Hrxn = +1300. kJ + 2(–394 kJ) + (–286 kJ)
C. –620 kJ
D. –226 kJ
E. 620 kJ
Your Turn!

Which reaction corresponds to the standard enthalpy

of formation of NaHCO3(s), ∆Hf ° = – 947.7 kJ/mol?

A. Na(s) + ½H2(g) + 3/2O2(g) + C(s, gr) → NaHCO3(s)

B. Na+(g) + H+(g) + 3O2–(g) + C4+(g) → NaHCO3(s)
C. Na+(aq) + H+(aq) + 3O2–(aq) + C4+(aq) → NaHCO3(s)
D. NaHCO3(s) → Na(s) + ½H2(g) + 3/2O2(g) + C(s, gr)
E. Na+(aq) + HCO3–(aq) → NaHCO3(s)
Your Turn!
The standard enthalpy of formation of sulfur dioxide is
-296.9 kJ. What is ∆H for the formation of 16.03 g of
sulfur dioxide in its standard state from its elements in
their standard states?

mol SO2 − 296.9 kJ

16.03 g SO2 × ×
64 g SO2 mol SO2

= ̶ 74.2 kJ
Your Turn!
Calculate ∆H for this reaction using ∆Hf° data.
2Fe(s) + 6H2O(l) → 2Fe(OH)3(s) + 3H2(g)
∆H f ° 0 –285.8 –696.5 0

∆Hrxn = 2×∆Hf°(Fe(OH)3, s) + 3×∆Hf°(H2, g)

– 2× ∆Hf°(Fe, s) – 6×∆Hf°(H2O, l )
∆Hrxn = 2 mol× (– 696.5 kJ/mol) + 3×0 – 2×0
– 6 mol× (–285.8 kJ/mol)
∆Hrxn = –1393 kJ + 1714.8 kJ
∆H rxn = 321.8 kJ
Your Turn!
Calculate ∆Hf° for FeO(s) using the information
below. ∆Hf° values are shown below each
substance.

Fe3O4(s) + CO(g)  3FeO(s) + CO2(g) ∆Ho=21.9 kJ

-1120.9 kJ -110.5 kJ ?? – 393.5 kJ

. 272.0 kJ
A

B. -816.0 kJ
C. -272.0 kJ
D. 26.00 J
E. -38.60 kJ
Coffee Cup Calorimetry
When 50.0 mL of 0.987 M H2SO4 is added to 25.0 mL of
2.00 M NaOH at 25.0 °C in a calorimeter, the temperature of
the aqueous solution increases to 33.9 °C. Calculate ∆H in
kJ/mole of limiting reactant. Assume: specific heat of the
solution is 4.184 J/g°C, density is 1.00 g/mL, and the
calorimeter absorbs a negligible amount of heat.
Write balanced equation
2NaOH(aq) + H2SO4(aq) → Na2SO4(aq) + 2H2O(aq)
Determine heat absorbed by calorimeter
masssoln = (25.0 mL + 50.0 mL) × 1.00 g/mL = 75.0 g
qsoln = 75.0 g × (33.9 – 25.0)°C × 4.184 J/g°C = 2.8×103 J
Determine Limiting Reagent
1 L H2 SO 4 0.987 mol H2 SO 4
50.0 mL H2 SO 4 × ×
1000 mL H2 SO 4 1 L H2 SO 4
= 0.04935 mol H2SO4 present

= 0.0987 mol NaOH

needed
1 L NaOH 2 mol NaOH
25.0 mL NaOH × ×
1000 mL NaOH 1 L NaOH
= 0.0500 mol NaOH present
NaOH is limiting
− 2.8 × 10 3 J 1 kJ
∆H = × = –56 kJ/mol
0.0500 mol NaOH 1000 J
78
Your Turn!
Pembakaran sempurna aseton (C3H6O) dinyatakan dengan
persamaan termokimia berikut. Mr aseton adalah 58.
C3H6O(l) + 4 O2(g) → 3 CO2(g) + 3 H2O(l) ∆H = - 1790 kJ
• Hitung kalor yang dihasilkan pada pembakaran sempurna
11,6 g aseton.
• Hitung kalor yang dihasilkan pada pembakaran aseton jika
pada pembakaran tersebut dihasilkan 3,6 g air.
• Hitung massa aseton yang harus dibakar agar kalor yang
dihasilkan cukup untuk memanaskan 100 g air dari 26oC
menjadi 100oC. Diketahui kalor jenis air adalah 4,2 J g-1
oC-1.
 Good Luck !!!
Confident in Your Answers

References:
Brady, J, E., Jepersen, N. D., Hyslop A., 2012, Chemistry, 7th Edition, International Student Version, John
Wiley and Sons.
Raymond Chang and Kenneth A. Goldsby, 2012, Chemistry, McGraw-Hill