How to describe changes of energy
in this reaction?
How much work was done for
expansion of gas?
How much energy was spent for
increase of temperature?
How internal energy changed ?
2 H2 (g) + O2 (g) => 2 H2O (g)
One possible approach is to compare internal energy
of substance before and after reaction
Internal energy of a substance is a sum of kinetic
and potential energies of all atoms in the sample
Kinetic Energy: energy of moving body
Potential Energy: energy that something has as a result
of its position and some force that is capable of changing
that position
PE = mgh
Nanoscale
Kinetic Energy: thermal energy – nanoscale
objects in motion (atoms, molecules, ions, etc.)
Potential Energy:electrostatic energy (coulombic
attraction between anions & cations) & chemical
potential energy (attractions among atomic nuclei
and electrons in molecules)
Units of Energy
The SI Unit for energy is the joule (J). Same as for work
The joule is an SI derived unit.
1 joule = 1 kg m2
s2
(Energy = Force x Distance)
It is frequently more practical to use a larger unit – the kilojoule (kJ)
1 kJ = 103 J
Units of Energy
Another common unit of energy is the calorie.
1 cal = 4.184 J
energy required to raise the temperature of 1 gram of water 1 degree Celsius
Energy changes related to most chemical processes
are reported in kilocalories (kcal) or kilojoules
(kJ).
1 kcal = 1000 cal = 4.184 kJ = 4184 J
System and Surroundings
it is helpful to define the sample
of matter you are investigating as
a system (eg. a reaction, an object,
etc.)
Anything that can exchange
energy with the system is
defined as a surroundings.
three types of systems:
An open system A closed system An isolated system
An open system can exchange mass and
energy with the surroundings.
System and Surroundings
three types of systems:
A closed system allows the transfer
of energy but not mass.
System and Surroundings
three types of systems:
An isolated system does not exchange
either mass or energy with its
surroundings.
Chapter 9.3
The first law of thermodynamics:
Conservation of Energy
Energy can be neither created nor destroyed – the total
energy of the universe is constant.
The total amount of energy must remain constant, so any
energy transferred out of the system must be transferred
into the surroundings, and vice versa.
Thermodynamic Changes
We will refer to ΔU (change in energy) when keeping track of
energy transfers.
ΔU = Ufinal - Uinitial
-The sign of ΔU indicates the direction of transfer.
ΔUsystem > 0 Energy transferred into the system.
- Final U greater than initial U
ΔUsystem < 0 Energy transferred out of the system.
- Final U lower than initial U
Endothermic vs. Exothermic
Processes involving energy transfers can be described as
endothermic or exothermic.
endothermic: energy is transferred into the system
exothermic: energy is transferred out of the system
Endothermic or Exothermic?
Melting Freezing
Chapter 9.4
Heat and Work
The first law of thermodynamics states that energy can be neither
created nor destroyed – the total energy of the universe is constant.
Energy is transferred from one form to
another and from one body to another.
Two ways to transfer energy are Heat q and Work w
Units of work are the same as units of energy
J, kJ, cal 1Joule = Pa*m3
Work and Heat
system is losing energy system is gaining energy
What is the change in the internal energy of a
system that did 7.02 kJ of work and absorbed 888
J of heat?
What is the change in the internal energy of a
system that did 5320 J of work and released 560 J
of heat?
Work done by expanding gas
negative sign
Where
P is the external opposing pressure
and ΔV is change of volume
Units of work are the same as
units of energy
J, kJ, cal
1Joule = Pa m3
The gas-forming reaction produced 2.5 m3 gas against a
constant pressure of 2.0 * 105 Pa.
Calculate the work done by the gas in Joules.
Work done by expanding gas
1. What is the work done by gas expanding toward the
vacuum?
2. There is some amount of gas produced by reaction carried
in the closed rigid vessel (at constant volume).
What is the work done by gas in this case?
Work done by expanding gas
1. What is the work done by gas expanding toward the vacuum?
w=0
2. There is some amount of gas produced by reaction carried
in the closed rigid vessel (at constant volume).
What is the work done by gas in this case?
w=0
Change of Internal energy
If process is conducted at constant volume
w=0 ΔU = qv
no work, change of internal energy resulting in heat produced
(or absorbed)
If process is conducted at constant pressure
w =-PΔV ΔU = qp - PΔV
qp = ΔU + PΔV
Heat of reaction is change of Internal energy of the system
plus the energy that is spend for expansion.
How to describe changes of energy
in this reaction?
How much work was done for
expansion of gas?
How much energy was spend for
increase of temperature?
How internal energy changed ?
2 H2 (g) + O2 (g) => 2 H2O (g)
Chapter 9.6
Enthalpy
Very often chemical processes are conducted in the open
systems (at constant pressure).
qp = ΔU + PΔV
Let's introduce new thermodynamic function: Enthalpy
H = U + PV
Change of enthalpy ΔH = ΔU + PΔV = qp
Enthalpy of reaction ΔH equals heat of reaction.
at constant pressure
Enthalpy
Enthalpy is a thermodynamic function
H = U + PV
Change of enthalpy ΔH = ΔU + PΔV
If reaction occurs under Vconst then PΔV = 0 and qv = ΔU
ΔH = ΔU
Most of reactions occurs under Pconst, where
ΔH = qp = ΔU + PΔV
The heat of reactions at Pconst (qp) is equal to ΔH and called
Enthalpy of reaction
State functions and
process functions
State function is a property of a system that depends only on the current
state of the system, not on the way in which the system acquired that state
(independent of path).
Process function (or path function) is a property of a system that does
depend on the way in which the system acquired particular state.
eg. Altitude is a state function.
State functions and
process functions
State function is a property of a Process function (or path function)
system that depends only on the is a property of a system that does
current state of the system, not on depend only on the way in which the
the way in which the system acquired system acquired particular state.
that state (independent of path).
Energy
Work
Pressure
Heat
Volume
Temperature Work and Heat reflect changes of energy.
Work and Heat have units of energy:
Enthalpy J or cal
Thermochemical equation
CH4(g) + 2O2(g) CO2(g) + 2H2O(l) ΔH = −890.4 kJ/mol
exothermic
“per mole” for ΔH means that this is the enthalpy change
per mole of the reaction as it is written.
ΔH= ΔHmolar * n
Find ΔH for reaction of 5.0 moles of CH4 with excess of O2 :
ΔH= -890.4 kJ/mol * 5.0mol
Endothermic vs. Exothermic
endothermic: energy is transferred into the system
ΔH>0
exothermic: energy is transferred out of the system
ΔH<0
Physical States of Matter
Physical states are important in thermochemical equations.
Phase changes are accompanied by enthalpy changes, so ΔH
depends on the phases of the reactants and products.
H2 (g) + ½ O2 (g) => H2O (g) ; ΔH = - 241.8 kJ/mol
H2 (g) + ½ O2 (g) => H2O (l) ; ΔH = - 285.8 kJ/mol
H2 (g) + ½ O2 (g) => H2O (g) ; ΔH = - 241.8 kJ/mol
2 H2 (g) + O2 (g) => 2 H2O (g) ; ΔH =
Manipulating Thermochemical Equations
When a thermochemical equation is multiplied by
any factor, the value of ΔH for the new equation
is obtained by multiplying the ΔH in the original
equation by that same factor.
H2 (g) + ½ O2 (g) => H2O (g) ; ΔH = - 241.8 kJ/mol
2 H2 (g) + O2 (g) => 2 H2O (g) ; ΔH = - 483.6 kJ/mol
Combustion of methane
CH4(g) + 2O2(g) CO2(g) + 2H2O(g) ΔH = − 802.4 kJ/mol
Reversed reaction
CO2(g) + 2H2O(g) CH4(g) + 2O2(g) ΔH =
Manipulating Thermochemical Equations
When a thermochemical equation is reversed, the
value of ΔH is reversed in sign.
Combustion of methane
CH4(g) + 2O2(g) CO2(g) + 2H2O(g) ΔH = − 802.4 kJ/mol
Reversed reaction
CO2(g) + 2H2O(g) CH4(g) + 2O2(g) ΔH = +802.4 kJ/mol
Given the equation:
3 O2 (g) => 2 O3 (g) ; ΔH = +285.4 kJ/mol
3/2 O2 (g) => O3 (g) ; ΔH = ?
H2 (g) + Cl2 (g) => 2 HCl (g) ; ΔH = -184.6 kJ/mol
4 HCl (g) => 2H2 (g) + 2Cl2 (g) ; ΔH = ?
Given the following equation:
N2 (g) + 3 H2 (g) => 2 NH3 (g); ΔH = -92.60 kJ/mol
Find ΔH for decomposition of 6 mol of ammonia gas.
When 0.250 mol of solid CaO is mixed with 0.250 mol of
liquid water, solid Ca(OH)2 is formed and 16.3 kJ of heat
is released. Write a thermochemical equation for the
reaction producing 1 mol of Ca(OH)2.
What is the enthalpy change when 22.5 g of CH4 are
burned in excess O2?
CH4(g) + 2 O2(g) => CO2(g) + 2 H2O(l); ΔH = -890 kJ/mol
Specific Heat Capacity and Heat Capacity
The specific heat (capacity), Cs, is the amount of heat
required to raise the temperature of 1 g of the substance
by 1°C. Unit is J/(g • °C). Sometimes reported as
molar heat capacity (J/(mol • °C).
Heat capacity (C) is the amount of heat required to raise
the temperature of an object by 1°C. Unit is J/°C
Heat capacity of the object can be found as
C = Cs • m
Calculate the heat capacity (in kJ) of an iron axe, m= 1.2kg
if specific heat Cs_iron=25.1 J/(mol • °C)
Specific Heat and Heat Capacity
The heat associated with a temperature change may be
calculated:
q = mCsΔT q = CΔT
m is the mass.
Cs is the specific heat.
ΔT is the change in temperature (ΔT = Tfinal – Tinitial).
C is the heat capacity.
Calculate the amount of heat (in kJ) required to heat 255 g
of water from 25.2°C to 90.5°C.
Specific heat Cs_water=4.184 J/(g • °C)
There was 5535J of heat transferred to the 150g sample
of ethanol at initial temperature 25 C. What is final
temperature of the ethanol?
Specific heat Cs_et=2.46J/(g • °C)
How to measure heat?
Calorimetry is the measurement
of heat changes.
Heat changes are measured in a
device called a calorimeter.
System: reactants and products (the reaction)
Surroundings: water in the calorimeter
Calorimetry
System: reactants and products (the reaction)
Surroundings: water in the calorimeter
qsys = - qsur
Heat passed to water:
qsur= mCsΔT
Heat of neutralization:
HCl(aq) + NaOH(aq) → H2O(l) + NaCl(aq)
Heat of fusion: H2O(s) → H2O(l)
Calculate heat of reaction performed in the calorimeter if T
increased from 23°C to 47°C. Mass of water is 24.0 g.
Cs_water = 4.184 J/g°C
A metal pellet with a mass of 100.0 g, originally at 88.4°C, is
dropped into 125 g of water originally at 25.1°C. The final
temperature of both pellet and the water is 31.3°C.
Calculate the heat capacity C (in J/°C) of the pellet.
Cs_water = 4.184 J/g°C
Heat capacity of the calorimeter
We can determine the heat capacity of
the calorimeter by measuring the heat of
the reaction with precisely known heat.
qrxn = -(qsur + qcal) = - (Cs_wmwΔT + qcal )
Heat of reaction of reaction was measured in the calorimeter.
Literature data for this reaction is ΔH=8568 J
Ti = 20
Tf = 40
Cs_water = 4.184 J/g°C
mwater =100g
52
Constant-pressure calorimeter
This type of calorimeter is an open system.
(not vacuum-tight)
That means that there is constant pressure 1atm.
Heat of process at Pconst :
qp = ΔH = ΔU + PΔV
When we measure heat of reaction in
the constant-pressure calorimeter we measure
enthalpy of reaction ΔH
Constant-volume calorimeter:
- Bomb calorimeter
Bomb calorimeter is usually used to measure
heat of combustion
qv = ΔU
When we measure heat of reaction in
the constant volume calorimeter we
measure Change in energy ΔU
When we measure heat of reaction in
the constant-pressure calorimeter we measure
enthalpy of reaction ΔH
qp = ΔH = ΔU + PΔV
When we measure heat of reaction in
the constant volume calorimeter we measure
Change in energy ΔU
qv = ΔU
ΔUrxn and ΔHrxn
The difference between ΔUrxn and ΔHrxn is usually
small.
ΔH = ΔU + PΔV
comparably small
2 H2 (g) + O2 (g) =>2 H2O (l) at25 C
ΔH = -571.6 kJ/mol ΔU = -564.2 kJ/mol
PΔV= 7.4 kJ/mol
How to find enthalpy of reaction without
measuring it experimentally?
Enthalpy is a state function.
Enthalpy of certain substance doesn't depend on the way it was
synthesized
Na(s) + 1/2Cl2(g) => NaCl(s)
NaCl(s) + H2O => NaCl(aq)
Enthalpy of reaction
ΔH = ΔH(products) – ΔH(reactants)
Hess’s Law
ΔHr = ΔH(products) – ΔH(reactants)
Hess’s law states that the change in enthalpy for a stepwise
process is the sum of the enthalpy changes for each of the
steps.
A + B => C + D ΔH1
C + D => E ΔH2
A + B => E ΔH3
ΔH1 + ΔH2 = ΔH3
G. H. Hess
Hess’s Law
3H2 + N2 => N2H4 ΔH1= 95.4kJ
N2H4 + H2 => 2NH3 ΔH2= -187.6kJ
4H2 + N2 => 2NH3 ΔH=ΔH1 + ΔH2=-92.2kJ
Hess’s Law
CH4(g) + 2O2(g) CO2(g) + 2H2O(l) ΔH = −890.4 kJ/mol
2H2O(l) 2H2O(g) ΔH = +88.0 kJ/mol
CH4(g) + 2O2(g) CO2(g) + 2H2O(g) ΔH = −802.4 kJ/mol
CH4(g) + 2O2(g)
Enthalpy
ΔH = −802.4 kJ
ΔH = −890.4 kJ
CO2(g) + 2H2O(g)
CO2(g) + 2H2O(l) ΔH = +88.0 kJ
Manipulation by thermochemical equations:
• You can add two or more equations together
adding their enthalpies at the same time.
You should cancel species on the different
sides of equation and add species on the same
side.
• Always specify the physical states of reactants and
products.
• When multiplying an equation by a factor (n), multiply
the ΔH value by same factor.
• Reversing an equation changes the sign but not the
magnitude of ΔH.
NO(g) + O3(g) → NO2(g) + O2(g) ΔH = –198.9 kJ/mol
3
O3(g) → O2(g) ΔH = –142.3 kJ/mol
2
O2(g) → 2O(g) ΔH = +495 kJ/mol
determine the enthalpy change for the reaction
NO(g) + O(g) → NO2(g)
Solution The first equation has NO as a reactant with the correct coefficients, so
we will use it as is.
NO(g) + O3(g) → NO2(g) + O2(g) ΔH = –198.9 kJ/mol
The second equation must be reversed so that the O3 introduced by the first
equation will cancel (O3 is not part of the overall chemical equation). We also must
change the sign on the corresponding ΔH value.
3
O (g) → O3(g) ΔH = +142.3 kJ/mol
2 2
These two steps sum to give:
NO(g) + O3(g) → NO2(g) + O2(g) ΔH = –198.9 kJ/mol
1 3
+ O2(g) O2(g) → O3(g) ΔH = +142.3 kJ/mol
2 2
1
NO(g) + O2(g) → NO2(g) ΔH = –56.6 kJ/mol
2
1
Solution We then replace 2O2 on the left with O by incorporating the last
equation. To do so, we divide the third equation by 2 and reverse its direction. As a
result, we must also divide ΔH value by 2 and change its sign.
1
O(g) → O2(g) ΔH = –247.5 kJ/mol
2
Finally, we sum all the steps and add their enthalpy changes.
NO(g) + O3(g) → NO2(g) + O2(g) ΔH = –198.9 kJ/mol
3
O (g) → O3(g) ΔH = +142.3 kJ/mol
2 2
1
+ O(g) → O2(g) ΔH = –247.5 kJ/mol
2
NO(g) + O(g) → NO2(g) ΔH = –304 kJ/mol
Think About It Double-check the cancellation of identical items–especially
where fractions are involved.
Find enthalpy of reaction:
2C2H2(g) + 5O2(g) → 4CO2(g) + 2H2O(l)
ΔH = ΔH(products) – ΔH(reactants)
What is enthalpy of ΔH(products)?
What is enthalpy of ΔH(reactants)?
Standard Enthalpy of formation
The standard enthalpy of formation (ΔH f°)
is defined as the heat change that results when 1 mole of a
compound is formed from its constituent elements in their
standard states.
C(graphite) + O2(g) CO2(g) ΔH f° = −393.5 kJ/mol
Enthalpy of formation of CO2
Elements in standard 1 mole of product
states
constituent elements
are the “sea level”
Standard Enthalpy of formation
The standard enthalpy of formation (ΔH f°) is defined as
the heat change that results when 1 mole of a compound is
formed from its constituent elements in their standard
states.
Standard state:
• 1 atm pressure for gases
• 1 M concentration for solutions
ΔHf° for an element
in its most stable form is zero.
ΔH f° - Appendix D in the textbook
Alotropes
Allotropes are different structural modifications of an
element; the atoms of the element are bonded together
in a different manner.
Carbon Phosphorus Arsenic
Diamond White Phosphorus Yellow Arsenic
Graphite Red Phosphorus grey Arsenic
Graphene Violet Phosphorus Black Arsenic
fullerene Black Phosphorus
Standard Enthalpy of reaction
Enthalpy of reaction depends on temperature and
on pressure.
We should specify T and P when writing
thermochemical equation.
The standard enthalpy of reaction (ΔH °rxn)
is defined as the enthalpy of a reaction carried
out under standard conditions.
standard conditions P = 1 atm
Calculation of
Standard Enthalpy of reaction
aA + bB → cC + dD
ΔH °rxn = [cΔH f° (C) + dΔH f° (D) ] – [aΔH f° (A) + bΔH f° (B)]
ΔH °rxn = ΣnΔH f° (products) – ΣmΔH f° (reactants)
n and m are the stoichiometric coefficients for the reactants and
products.
Given the following information, calculate the standard enthalpy of
formation of acetylene (C2H2) from its constituent elements:
C(graphite) + O2(g) → CO2(g) ΔH°rxn = –393.5 kJ/mol (1)
1
H2(g) + O2(g) → H2O(l) ΔH°rxn = –285.5 kJ/mol (2)
2
2C2H2(g) + 5O2(g) → 4CO2(g) + 2H2O(l) ΔH°rxn = –2598.8 kJ/mol (3)
Chemical Energy
• In an exothermic chemical reaction (ΔH < 0),
where does the energy come from?
• In an endothermic reaction (ΔH > 0), where does
the energy go?
• In a chemical reaction, chemical bonds are
broken, and new chemical bonds are formed.
• As nuclei and electrons move closer together or
further apart, their energies change.
Bond Enthalpies
• Bond Enthalpy (Bond Energy): the enthalpy
change that occurs when two bonded atoms in a
gas-phase molecule are separated completely at
constant pressure
– Bond breaking is always an endothermic
process – energy must be put in to break a
chemical bond.
– Bond enthalpies are always positive.
The potential energy of atoms are lower when
they are bonded together.
Bond Enthalpies
The bond enthalpy is the enthalpy change associated with
breaking a bond in 1 mole of gaseous molecule.
H2(g) → H(g) + H(g) ΔH° = 436.4 kJ/mol
H-H (g) → H(g) + H(g)
The enthalpy for a gas phase reaction is given by:
ΔH° = ΣBE(reactants) – ΣBE(products)
ΔH° = total energy input – total energy released
bonds broken bonds formed
Bond Enthalpies
•Bond breaking is always endothermic:
Cl2 (g) => 2 Cl (g) ; ΔH = + 242 kJ
•Bond formation (the reverse reaction) is always exothermic:
2 Cl (g) => Cl2 (g); ΔH = - 242 kJ
•Bond enthalpies are usually expressed per mole of bonds.
eg. The bond enthalpy (bond strength) of Cl2 is
+242 kJ/mol.
These are average
enthalpies of bonds in the
polyatomic molecules.
Knowing the bond
enthalpies for the bonds
broken & formed in a
chemical reaction allows
you to predict whether
the reaction will be
endothermic or
exothermic.
Use the table of bond enthalpies to answer the questions.
a) Which of the molecules in the table has the strongest bond? The weakest
bond?
b) Calculate the enthalpy change for the following reactions:
H-H + Br-Br → 2 H-Br
H-H + F-F → 2 H-F
Bond Bond Enthalpy
c) Which is the most exothermic?
(kJ/mol) _
H-H 436
H-Br 366
H-F 566
Br-Br 193
F-F 158
Estimate the enthalpy of reaction for the combustion of methane:
(use the table in the appendix)
CH4(g) + 2O2(g) → CO2(g) + 2H2O(l)
Chapter 9.11 Lattice Energy
• The lattice energy is the energy released when the solid
crystal forms from separate ions in the gas state.
– Always exothermic
– Hard to measure directly, but can be calculated from
knowledge of other processes
© 2015 Pearson Education, Inc.
• Lattice energy depends directly on the size of charges and
inversely on distance between ions.
– Larger ion = weaker attraction
– Weaker attraction = smaller lattice energy
© 2015 Pearson Education, Inc.
Trends in Lattice Energy: Ion Charge
• The force of attraction between oppositely charged particles is directly
proportional to the product of the charges.
• Larger charge means the ions are more strongly attracted.
– Larger charge = stronger attraction
– Stronger attraction = larger lattice energy
• Of the two factors, ion charge is generally more important.
© 2015 Pearson Education, Inc.
Lattice Energy through Born-Haber cycle
A Born-Haber cycle is a cycle of reactions used to
determine the lattice energy of an ionic compound
Na(s) + 1 Cl2(g) → Na+(g) + Cl-(g)
2
Step 1 Formation of gaseous sodium from solid sodium.
Na(s) => Na(g) b ∆H°1= (sublimation energy of Na) = +108 kJ
Step 2 Formation of an atomic chlorine.
1/2 Cl2(g) => Cl(g) ∆H°2 = (bond energy of Cl*1/2 ) = +122 kJ
Step 3 Ionization of gaseous sodium. the ionization energy of sodium.
Na(g) => Na+(g) + e- ∆H°3 = (ionization energy of Na) = +496 kJ
Step 4 Addition of an electron to gaseous chlorine.
Cl(g) + e- => Cl-(g) ∆H°4 =(electron affinity of Cl) = -349 kJ
Step 5 Formation of the crystalline solid from the gaseous ions. The
enthalpy change for this step is the lattice energy.
Na+(g) + Cl-(g) => NaCl(s) ∆H°5 = ∆H°lattice = ?
∆H°f = ∆H°step 1 + ∆H°step 2 + ∆H°step 3 + ∆H°step 4 + ∆H°step 5
∆H°lattice = ∆H°step 5 = ∆H°f - (∆H°step1 + ∆H°step 2 + ∆H°step 3 + ∆H°step 4) =
-411kJ - (+108kJ + 122kJ + 496kJ - 349kJ) = -788kJ
When calculating ionization energy (step3) and electron affinity energy make sure to use
proper value:
Ca(g) => Ca2+(g) ΔH = 1st IE + 2nd IE
Chapter 9
Thermochemistry
© 2015 Pearson Education, Inc.
