Energetics

IB Topics 5

PART 2: Calculating H via Bond Enthalpies & Hess’s

Law
Different Ways to Find H
Last section covered how to find H
using calorimetry
Another way is to use literature values in
the Data Booklet where you look up:
Standard Enthalpy of Formation and
Standard Enthalpy of Combustion
STANDARD ENTHALPY CHANGE OF FORMATION,
Hf
Definition:
The enthalpy change when one mole of
the compound is formed from its elements
in their standard states ( 298 K and 1 atm
of pressure.)
In essence, Formation reactions are
synthesis reactions where a compound is
formed from its elements
STANDARD ENTHALPY CHANGE

OF FORMATION, Hf
It’s very difficult to measure Formation
values in the lab so we need to use data
booklet values instead
These values have some assumptions
that go with them:
◦ a. Values are measured in standard states
◦ b. Make sure the reactants are written in
elemental form
◦ c. These values are per 1 mole of product
formed
a. STANDARD STATE MEANS…

It is the pure form of the substance at :

T= 298K (25oC) and P= 1 atm (100 kPa)
EX: Under these conditions, water is a
liquid so it’s standard state is liquid, not
solid or gas
Metals will be solid, and gases are gases
Note Standard state is different temp.
from STP (0oC)
 Hf
b. For , reactants need to be in elemental form

Need to know which elements are diatomic

or otherwise
EX: Oxygen is O2, just like the rest of the
‘magic 7’
Phosphorous is P4
Sulfur is S8,
Pretty much everything else is ‘by itself’
like Mg, Ca, etc.
 C has many allotropes but graphite is the
standard one because it’s more stable than
 
H
c. f Values are per One Mole
EXAMPLE: Write the equation for the
formation of Ag2S
Thismeans write the synthesis equation for
Ag2S being the product
The elements that make it up are:
 Ag + S  Ag2S
Make sure the elements are written in
standard state
Ag(s) + S8 (s)  Ag2S(s)
◦ Sulfur is S8 and since Ag2S is ionic, must be a
 
H
c. f Values are per One Mole
Balance it normally to get:
16Ag(s) + S8 (s)  8Ag2S(s)
Product needs to be per ONE mole so
divide accordingly (by 8):
2Ag(s) + S8 (s)  1Ag2S(s)
STANDARD ENTHALPY CHANGE

OF COMBUSTION, H c

Definition:
theenthalpy change when one mole of a
substance is completely combusted in
oxygen under standard conditions.
Values found in Section 13 of Data
Booklet. Notice all values are negative
because they are exothermic—because
combustion releases energy
 STANDARD ENTHALPY CHANGE
OF COMBUSTION
Similar assumptions as Enthalpy of
Formation, difference is it is a combustion
reaction:
 All substances need to be in standard state
Needs to show ONE mole of reactant being
combusted
◦ so coefficients need to be adjusted accordingly
with fractions, if necessary)
 STANDARD ENTHALPY CHANGE
OF COMBUSTION
EX- Write the Combustion equation of CH4 in
the proper format

CH4 (g) + 2O2 (g)  CO2(g) + 2H2O(l)

Note :
only one mole of CH4 combusted
Chemicals in standard state (see water!)
Are these Reactions Written Properly
for and ? Δ HΘ Hf
c

Mg (l) + Cl (g)  MgCl2 (aq) for H f

 No, Mg is not in standard state. Is a solid at 25 degrees

N2(g) + O2(g)  2NO(g) for Hf

H f
 No, Θ
is for ONE mole of product formed
ΔH c
 CH3OH(l) + O2(g)  2H2O (g) + CO2 (g) for
Θ
 No, H2O is not in standard state—needs to be liquid
Δ Hc
2CO (g) + O2 (g)  2CO2 (g) for
 No, needs to be ONE mole of reactant combusted
 Calculating Enthalpy Change for
reactions using values
Hf

Last section we found ΔH values using a

calorimeter. They can be found using
values in Data Booklet as well using this
formula: 
Reaction enthalpy =
(sum of enthalpy of formation of the prod) -
(sum of enthalpy of formation of the rxts)
OR
ΔH = ∑ ΔHf (prod) - ∑ ΔHf (rxts)
Look in this column for
Enthalpy of Formation Data
Enthalpy of Formation Calculations
See Section 12 of Data Booklet for
values – need to look carefully.

The BIG THING to notice is…


Hf values for elements are always
zero!!
because they can’t get ‘formed’ from
anything simpler than what they already
are
Enthalpy of Formation Example
Given these standard enthalpy change values (kJ mol−1):
 ΔHf [NH3(g)] = −46
 ΔHf [NO(g)] = 90
 ΔHf [H2O(g)] = −242
 Calculatethe enthalpy change for the reaction:
 4NH3(g) + 5O2(g) → 4NO(g) + 6H2O(g)
 ΔH = ∑ ΔHf (products) - ∑ ΔHf (reactants)
 ΣΔHf (products) = (4 × 90) + (6 × −242) = −1092 kJ mol−1
 ΣΔHf (reactants) = 4 × −46 = −184 kJ mol−1
 Note: ΔH f for O2(g) is zero because it is an element in its standard
state.
 ΔH = −1092 − (−184) = −908 kJ mol−1
 So the enthalpy change for this reaction is −908 kJ mol−1
 EX- Calculate the enthalpy change for the
combustion of one mole of CH3OH.

Even though it’s a combustion reaction, still look up Hf data. data is only
used for comparison to experimental or other data.

1. Write the balanced equation:

◦ 2CH3OH(l) + 3O2(g) → 2 CO2(g) + 4H2O (l)
◦ Change to 1 mole of methanol
◦ 1CH3OH(l) + 3/2 O2(g) → 1CO2(g) + 2H2O (l)
◦ 2. Ensure in Standard State

◦  H
3. Lookup f values, plug into equation and
multiply values by coefficient (Section 12)
◦ ΔH = ∑ ΔHf (products) - ∑ ΔHf (reactants)
EX- Calculate the enthalpy change for
the combustion of one mole of CH3OH.

Note: There is no value for oxygen because

it’s in elemental form so it’s Hf value is zero
◦ ΔH = [ 1(-393.5) + 2(-285.8)] - [1(-239)]
◦ = -965.1 - -239
◦= -726.1 kJ/mol
 HESS’ LAW
Sometimes it’s hard to find the enthalpy change of a
reaction for a variety of reasons
But if the main path is blocked, might need to take a
detour which takes you to other paths
Germain Hess found this was true for reactions
The value of H for a reaction is the same whether it
occurs in one step or in a series of steps.


 HESS’ LAW

If A toD can’t be determined, the side

reactions can be calculated instead
H for the overall equation is the sum of the
H’s for the individual steps.
Hrxn = H1 + H2 + …
Overall enthalpy change is constant and
doesn’t depend on pathway taken
 HESS’ LAW
There are two methods---equation method or
energy cycle method
For example: Ice sublimating directly to Steam
If this direct route cannot be found, can try the
other side routes of:
Ice to Water and then
Water to Steam
Hess Law Example
EX- Using Hess’s Law, calculate the enthalpy of reaction, Hrxn, for the formation
of carbon monoxide from its elements
C(s) + ½ O2 (g)  CO(g) Hrxn = ?

Given: C(s) + O2(g)  CO2(g) H1 = -394 kJ/mol

CO(g) + ½ O2 (g)  CO2(g) H2 = -283 kJ/mol

EQUATION METHOD=Use the given

intermediate steps to equal the overall rxn
(in bold) by
multiplying/dividing/flipping them to
match where the prod and rxts need to go
for the overall equation
Like a system of equations in Math
EX- Using Hess’s Law, calculate the enthalpy of reaction, Hrxn, for the formation
of carbon monoxide from its elements
C(s) + ½ O2 (g)  CO(g) Hrxn = ?

Given: C(s) + O2(g)  CO2(g) H1 = -394 kJ/mol

CO(g) + ½ O2 (g)  CO2(g) H2 = -283 kJ/mol
Keep rxn 1
C(s) + O2(g)  CO2(g) -394
Need to flip rxn 2. This means enthalpy sign also
flips from neg to pos
CO2(g)  CO(g) + ½ O2 (g) +283

Cancel chemical on opposite sides of arrow CO2(g) and ½ O2

That leaves us with

C(s) + ½ O2 (g)  CO(g)

Add up values
On Your Own: Calculate the enthalpy of reaction, Hrxn, for
the formation of nitrogen monoxide from its elements

N2 + O2  2NO Hrxn = ?

Using these equations:

4NH3 + 3O2  2N2 + 6H2O H = -1530 kJ flip

4NH3 + 5O2  4NO + 6H2O H = -1170 kJ

2N2 + 6H2O  4NH3 + 3O2 H = +1530 kJ

2N2 + 2O2  4NO H = +360 kJ 2
N2 + O2  2NO H =+180 kJ
 HESS’ LAW ENERGY CYCLES
An alternative to the equation method is using
energy cycles
Remember:
“Clock-wise = Counter-clock wise”

A H2
H1 C H1 = H2 + H3
H3
B
 Example

If Hfusion = 6.01 kJmol-1

and Hsublimation = 51.08 kJmol-1
What is Hvaporization?
Clockwise =counterclockwise
Hfusion + Hvaporization = Hsublimation
6.01 + Hvaporization = 51.08
Hvaporization= 45.07 kJmol-1
Example: Calculate the standard enthalpy change when one mole of
methane is formed from its elements in their standard states. The standard
enthalpies of combustion ( Hc hydrogen and methane are -
) of carbon,
393, -286 and -890 kJ mol-1 respectively.
 Step 1: Write the equation for enthalpy change with the
unknown H value. Call this value Hx.

Hx
C(s) + 2H2(g) CH4(g)
Example: Calculate the standard enthalpy change when one mole of
methane is formed from its elements in their standard states. The standard
enthalpies of combustion ( Hc hydrogen and methane are -
) of carbon,
393, -286 and -890 kJ mol-1 respectively.
 Step 2: Construct an energy cycle showing the different
routes to the products (in this case the products of
combustion).
Hx
C(s) + 2H2(g) CH4(g)

O2(g) O2(g)
2O2(g)
CO2(g) + 2H2O(g)
Example: Calculate the standard enthalpy change when one mole of
methane is formed from its elements in their standard states. The standard
enthalpies of combustion ( Hc hydrogen and methane are -
) of carbon,
393, -286 and -890 kJ mol-1 respectively.
 Step 3: Use Hess’ Law to equate the energy changes for
the two different routes.
Hx
C(s) + 2H2(g) CH4(g)

O2(g) O2(g)
2O2(g)
CO2(g) + 2H2O(g)

Hc (C)  2Hc (H2 )  Hx  Hc (CH4 )

Counter clockwise clockwise

Example: Calculate the standard enthalpy change when one mole of
methane is formed from its elements in their standard states. The standard
enthalpies of combustion ( Hc hydrogen and methane are -
) of carbon,
393, -286 and -890 kJ mol-1 respectively.
 Step 4: Substitute values and then solve for the unknown
H value.
   
H (C)  2H (H2 )  H
c c x  H (CH4 )
c

-393 + 2(-286) = + + -890

Hx   393  2(-286) - (-890)

Hx   75 kJ mol -1
BOND ENTHALPIES
 There’s one more way to find enthalpies and this is
using BOND ENTHALPIES
 Definition of Bond Enthalpy:
 The amount of energy needed to break one mole of
covalently bonded gaseous molecules @ standard
conditions
X-Y(g) ↔ X(g) + Y(g)
These values are on another page of the Data Booklet
These values are averages based on many assumptions
so they may not be perfectly accurate
That’s why they are referred to as average bond
enthalpies
BOND ENTHALPIES
Breaking bonds:
requires energy to overcome the attractive forces
holding the bond
H = positive (endothermic)

Forming bonds:
Releases energy
H = negative (exothermic)
 Calculating H from bond enthalpies:

In a rxn:
◦ Rxts bonds must break (endothermic)
◦ Atoms rearrange
◦ New products bonds form (exothermic)
◦ Whichever part (break or form) involves more energy
determines if rxn is endo or exothermic
◦ Need to use the enthalpy of each bond to find Hrxn
 Hrxn = (rxts bonds broken) - (prod bonds formed)

*(note, its not like enthalpy of formation

formula which is prod – rxts)
Table of bond enthalpies (Sec 10)

Single Bonds Double Bonds Triple Bonds

H-H 436 C=C 612 C≡C 837
C-C 348 O=O 496 N≡N 944
C-H 412
O-H 463
N-H 388
N-N 163

What do you notice about bond strength as number of bonds increase?

Calculating H from bond enthalpies:
Steps to calculate bond enthalpies:
1. Draw out structural formulas for rxts
and products
2. Account for bond types
(single,double,triple)
3. Look up bond enthalpies
4. Substitute enthalpies into formula
 Example: Calculate H for the
Single Bonds Double Bonds Triple Bonds
H-H 436 C=C 612 C≡C 837
C-C 348
C-H 412
O=O 496 N≡N 944
hydrogenation (adding H’s) of
O-H 463
N-H 388 ethene
N-N 163

(g) + HH (g) (g)

Energy absorbed to break bonds: Energy released as bonds form:

C=C 612 C-C 348
4 C-H 4 x 412 2696 kJ 6 C-H 6 x 412 2820 kJ
H-H 436
There is more energy released than absorbed,
so the rxn is exothermic.
Hrxn = (bonds broken) - (bonds formed)

H = 2696 – 2820 = -124 kJ mol-1

 Single Bonds Double Bonds Triple Bonds
H-H 436 C=C 612 C≡C 837 On Your Own: Calculate H for the
C-C 348
C-H 412
O=O 496 N≡N 944
combustion of hydrazine (N2H4) in oxygen.
O-H 463
N-H 388
This reaction has been used to power
N-N 163 spacecraft.

(g) + O=O (g) N≡N (g) + 2 (g)

Energy absorbed to break bonds: Energy released as bonds form:

N-N 163 N≡N 944
4 N-H 4 x 388 2211 kJ 4 O-H 4 x 463 2796 kJ
O=O 496

There is more energy released than absorbed,

so the rxn is exothermic.
Hrxn = (bonds broken) - (bonds formed)
H = 2211 – 2796 = -585 kJ mol-1
Limitations of Using
Average Bond Enthalpies
Single Bonds Double Bonds Triple Bonds
H-H 436 C=C 612 C≡C 837
C-C 348 O=O 496 N≡N 944
C-H 412
O-H 463
N-H 388
N-N 163
Look at the C-H bond value. How did they
arrive at that??
C-H bond is very common and appears in all
sorts of situations.
Limitations of Using
Average Bond Enthalpies

The C-H bond appears in different environments. These

environments have an effect on the energy needed to break
the bond (bond enthalpy)
How can it be the same value in all these situation?
It can’t. This value is an AVERAGE of all the chemicals
the bond is found in
 Average Bond Enthalpy vs Dissociation
Bond Enthalpy

EX- To determine the ave bond enthalpy for the C-H bond we find
the energy needed to break one mole of the bonds to give separated
atoms. This is called dissociation bond enthalpy .
To be consistent, everything must be in the gaseous state.
EX: Methane, CH4, contains four identical C-H bonds.
However, if you break CH4 to pieces one Hydrogen at a time, you
will have to supply a different amount of energy to break each bond.
Each time you break a C-H bond, the environment of those left
behind changes and the strength of a bond is affected by what else is
around it.
Average Bond Enthalpy vs Dissociation
Bond Enthalpy
For CH4 breaking the first bond looks like this:
CH4  CH3 + H   ΔH = +435 kJ
which is different from the energy change required for
breaking the 2nd bond:
CH3  CH2 + H   ΔH = +444 kJ
Here is the 3rd: CH2  CH + H   ΔH = +444 kJ
And the 4th: CH  C + H   ΔH = +339 kJ
The average of the four above bond dissociation
enthalpies above is:
(435 + 444 + 444 + 339)/4 = +415.5 kJ
This average value is called the average bond
enthalpy, or bond enthalpy term for C-H.
Average Bond Enthalpy vs Dissociation
Bond Enthalpy
So instead of writing out 4 different equations of this:
CH4  C + 4H
the average bond enthalpy equation can be shown as
the above divided by 4 to show its an average of those
4 reactions. (4 because there are 4 bonds needed to be
broken)  
¼ CH4(g)→ ¼ C(g) + H(g)
-make sure they are all in gas state

Try: Write the Bond Enthalpy equation for NH3

NH3(g)→ N(g) + 3H(g)
NH3(g)→ N(g) + H(g)
Limitations of Using
Average Bond Enthalpies
Another limitation is that average bond
enthalpies can only be used if all reactants and
products are gases.
EX: CH4(g) +2O2(g)  CO2(g) + 2H2O(l)
 H2O is a liquid here, needs to be a gas
 means even more energy is needed to convert the liquid
into gas (Hvap (vaporization) –an extra 41kJmol -1)
Thus, H values obtained using average bond
enthalpies are not necessarily very accurate.
Factors Affecting Bond Enthalpies
1. Bond length
Larger atoms when bonded have longer
lengths they have more e- so there’s
more repulsion nucleus is shielded
more results in weaker bond
Factors Affecting Bond Enthalpies
2. Number of Bonding Electrons
More bonding electrons more electrons
involved in the bond the stronger the
bond
Think of bonding e- as ‘gluing’ atoms
together—the more ‘glue’ the harder to
break apart
Factors Affecting Bond Enthalpies
3. Bond Polarity
The greater the Electronegativity
difference  the greater the charge  the
greater the attraction the stronger the
bond
OZONE
https://www.youtube.com/watch?v=Q__ZaATW
d5g
Watch video on your own and take notes.
Read text as well.