GEN.

CHEMISTRY 2 Q3-
WEEK 7
A Project By:
Shekinah Faith Ponay
Kathleen S. Carbonera
OBJECTIVES:

● Explain the First Law of Thermodynamics

● Explain enthalpy of a reaction

● Calculate the change in enthalpy of a given reaction

using Hess Law
LESSON 1:THE FIRST LAW OF THERMODYNAMICS
The First Law of Thermodynamics states that
“energy cannot be created nor destroyed”.

It can be transformed into another form but the total

amount of energy remains the same.
How energy is conserved is shown when you eat
your meal.
The chemical energy in the food will be converted into
mechanical energy that enables you to perform your
daily task.
But not all the chemical energy from the food you take
will be transformed into mechanical energy.
Some of it will be released from your body as heat when
you sweat or feel warm. In this law we talk of energy,
work and heat.
What is the first law of Thermodynamics?

Many power plants and engines operate by turning

heat energy into work.
The reason is that a heated gas can do work on
mechanical turbines or pistons, causing them to
move.
The first law of thermodynamics applies the
conservation of energy principle to systems where
heat transfer and doing work are the methods of
transferring energy into and out of the system.
The first law of thermodynamics states that the
change in internal energy of a system
ΔU equals the net heat transfer into the system Q,
plus the net work done on the system W.
In equation form, the first law of thermodynamics is,
ΔU=Q+W
Here ΔU is the change in internal energy U of the
system. Q is the net heat transferred into the system
—that is, Q is the sum of all heat transfer into and
out of the system. W is the net work done on the
system
So positive heat Q adds energy to the system and
positive work W adds energy to the system.
This is why the first law takes the form it does,
ΔU=Q+W.
It simply says that you can add to the internal energy
by heating a system, or doing work on the system.
What do each of these terms ( ΔU, Q, W)
mean?
Nothing quite exemplifies the first law of
thermodynamics as well as a gas (like air or helium)
trapped in a container with a tightly fitting movable
piston (as seen below).
We'll assume the piston can move up and down,
compressing the gas or allowing the gas to expand
(but no gas is allowed to escape the container).
The gas molecules trapped in the container are the
"system". Those gas molecules have kinetic energy.
 [Can a gas molecule have potential energy?]

The internal energy U of our system can be thought of as

the sum of all the kinetic energies of the individual gas
molecules.
So, if the temperature T of the gas increases, the gas
molecules speed up and the internal energy U of the gas
increases (which means ΔU, is positive).
Similarly, if the temperature T of the gas decreases, the
gas molecules slow down, and the internal energy U of
the gas decreases (which means ΔU is negative).
It's really important to remember that internal energy
U and temperature T will both increase when the
speeds of the gas molecules increase, since they
are really just two ways of measuring the same
thing; how much energy is in a system.
Since temperature and internal energy are
proportional T ∝U, if the internal energy doubles the
temperature doubles.
Similarly, if the temperature does not change, the
internal energy does not change.
One way we can increase the internal energy U (and
therefore the temperature) of the gas is by
transferring heat Q into the gas.
We can do this by placing the container over a
Bunsen burner or submerging it in boiling water.
The high temperature environment would then
conduct heat thermally through the walls of the
container and into the gas, causing the gas
molecules to move faster.
 If heat enters the gas, Q will be a positive number.
Conversely, we can decrease the internal energy of
the gas by transferring heat out of the gas.
We could do this by placing the container in an ice
bath.
If heat exits the gas, Q will be a negative number.
This sign convention for heat Q is represented in the
image below.
Since the piston can move, the piston can do work
on the gas by moving downward and compressing
the gas.
The collision of the downward moving piston with the
gas molecules causes the gas molecules to move
faster, increasing the total internal energy.
If the gas is compressed, the work done on the gas
W on gas is a positive number.
Conversely, if the gas expands and pushes the
piston upward, work is done by the gas
The collision of the gas molecules with the receding
piston causes the gas molecules to slow down,
decreasing the internal energy of the gas.
If the gas expands, the work done on the gas W on
gas is a negative number.
This sign convention for work W is represented in
the image below.
Below is a table that summarizes the signs
conventions for all three quantities (ΔU,Q,W)
discussed above.
ΔU Q W
(change in internal (Heat) (Work done on
energy) gas)
is + if temperature is + if heat enters is + if gas is
T increases gas compressed

is - if temperature is - if heat exits is - if gas expands

decreases gas

is 0 if temperature is 0 if no heat is 0 if volume is

T is constant exchanged constant
Is heat Q the same thing as temperature T?

Absolutely not.
This is one of the most common misconceptions
when dealing with the first law of thermodynamics.
The heat Q represents the heat energy that enters a
gas (e.g. thermal conduction through the walls of the
container)
The temperature T on the other hand, is a number
that's proportional to the total internal energy of the
gas.
So, Q is the energy a gas gains through thermal
conduction, but T is proportional to the total amount
of energy a gas has at a given moment.
The heat that enters a gas might be zero (Q=0) if the
container is thermally insulated, however, that does
not mean that the temperature of the gas is zero
(since the gas likely had some internal energy to
start with).
To drive this point home, consider the fact that the
temperature T of a gas can increase even if heat Q
leaves the gas.
This sounds counterintuitive, but since both work
and heat can change the internal energy of a gas,
they can both affect the temperature of a gas
For instance, if you place a piston in a sink of ice
water, heat will conduct energy out the gas.
However, if we compress the piston so that the work
done on the gas is greater than the heat energy that
leaves the gas, the total internal energy of the gas
will increase.
What do solved examples involving the first law of
thermodynamics look like?
Example 1: Nitrogen piston

A container has a sample of nitrogen gas and a

tightly fitting movable piston that does not allow any
of the gas to escape. During a thermodynamics
process, 200 joules of heat enter the gas, and the
gas does 300 joules of work in the process.
What was the change in internal energy of the gas
during the process described above?
Solution:
We'll start with the first law of thermodynamics.

● ΔU=Q+W
(start with the first law of thermodynamics)

● ΔU=(+200 J)+W (plug in Q=+200 J)

[Why is heat a positive number here?]
 ● ΔU=(+200 J)+(−300 J) (plug in W=−300 J)
[Why is work a negative number here?]

● ΔU=−100 J (calculate and celebrate)

Note: Since the internal energy of the gas
decreases, the temperature must decrease as well.
 Example 2 : Heating helium

Four identical containers have equal amounts of

helium gas that all start at the same initial
temperature. Containers of gas also have a tightly
fitting movable piston that does not allow any of the
gas to escape. Each sample of gas is taken through
a different process as described below:
Sample 1: 500 J of heat exits the gas and the gas
does 300 J of work

Sample 2: 500 J of heat enters the gas and the gas

does 300 J of work
Sample 3: 500 J of heat exits the gas and 300 J of
work is done on the gas

Sample 4: 500 J of heat enters the gas and 300 J of

work is done on the gas
Which of the following correctly ranks the final
temperatures of the samples of gas after they're
taken through the processes described above.
A. T4>T3>T2>T1
B. T1>T3>T2>T4
​
C. T4>T2>T3>T1

D. T1>T4>T3>T2​
Solution:
Whichever gas has the largest increase in internal
energy ΔU will also have the greatest increase in
temperature ΔT (since temperature and internal
energy are proportional). To determine how the
internal energy changes, we'll use the first law of
thermodynamics for each process.
Process 1:

ΔU = Q+W

ΔU = (-500J) + (-300J)

ΔU = -800 J
​
Process 2:

ΔU = Q+W

ΔU = (+500J) + (-300J)

ΔU = +200 J
​
Process 3:

ΔU = Q+W

ΔU = (-500 J) + (300 J)

ΔU = -200 J
​
Process 4:

ΔU = Q+W

ΔU = (+500 J) + (+300 J)

ΔU = +800 J
​
The final temperatures of the gas will have the same
ranking as the changes in internal energy (i.e.
sample 4 has the largest increase in internal energy,
so sample 4 will end with the largest temperature).
ΔU 4 >ΔU2 >ΔU3 >ΔU1 and T4>T2>T3>T1

​
So the correct answer is C.
LESSON 2:THE ENTHALPHY OF A REACTION
The change in energy (ΔU) is equal to the sum of
the heat produced and the work performed.
Work done by an expanding gas is called pressure-
volume work, (or just PV work).
 Consider, for example, a reaction that produces a
gas, such as dissolving a piece of copper in
concentrated nitric acid. The chemical equation for
this reaction is as follows:

Cu(s)+4HNO3(aq)→Cu(NO3)2(aq)+2H2O(l)+2NO2
If the reaction is carried out in a closed system that
is maintained at constant pressure by a movable
piston, the piston will rise as nitrogen dioxide gas is
formed
The system is performing work by lifting the piston
against the downward force exerted by the
atmosphere (i.e., atmospheric pressure).
We find the amount of PV work done by multiplying
the external pressure P by the change in volume
caused by movement of the piston (ΔV).

At a constant external pressure (here, atmospheric

pressure),

W = −PΔV
 The negative sign associated with PV work
done indicates that the system loses energy when
the volume increases.
 If the volume increases at
constant pressure (ΔV>0), the work
done by the system is negative,
indicating that a system has lost
energy by performing work on its
surroundings.
 Conversely, if the volume
decreases (ΔV<0), the work done by
the system is positive, which means
that the surroundings have performed
work on the system, thereby increasing
its energy.
Work Performed by a Reaction Carried
out at Constant Pressure
The figure above is an Example of Work Performed
by a Reaction Carried Out at Constant Pressure. (a)
Initially, the system (a copper penny and
concentrated nitric acid) is at atmospheric pressure.
(b) When the penny is added to the nitric acid, the
volume of NO2 gas that is formed causes the piston
to move upward to maintain the system at
atmospheric pressure. In doing so, the system is
performing work on its surroundings
The internal energy U of a system is the sum of the
kinetic energy and potential energy of all its
components. It is the change in internal energy that
produces heat plus work.
To measure the energy changes that occur in
chemical reactions, chemists usually use a related
thermodynamic quantity called enthalpy (H) (from
the Greek enthalpein, meaning “to warm”).
The enthalpy of a system is defined as the sum of its
internal energy U plus the product of its pressure P
and volume V:

H=U+PV
Because internal energy, pressure, and volume are
all state functions, enthalpy is also a state function.
So we can define a change in enthalpy (ΔH)
accordingly
ΔH=Hfinal−Hinitial
If a chemical change occurs at constant pressure
(i.e., for a given P, ΔP=0), the change in enthalpy
(ΔH) is

ΔH=Δ(U+PV)
=ΔU+ΔPV
=ΔU+PΔV
Substituting q+w for ΔU (First Law of
Thermodynamics) and −w for PΔV , we obtain

ΔH=ΔU+PΔV
=qp+w−w
=qp
The subscript p is used here to emphasize that this
equation is true only for a process that occurs at
constant pressure.
From Equation above we see that at constant
pressure the change in enthalpy, ΔH of the system,
is equal to the heat gained or lost.

ΔH=Hfinal−Hinitial=qp
Just as with ΔU, because enthalpy is a state
function, the magnitude of ΔH depends on only the
initial and final states of the system, not on the path
taken.
Most important, the enthalpy change is the same
even if the process does not occur at constant
pressure.

To find ΔH for a reaction, measure qp.

When we study energy changes in chemical
reactions, the most important quantity is usually the
enthalpy of reaction (ΔHrxn)

the change in enthalpy that occurs during a reaction

(such as the dissolution of a piece of copper in nitric
acid)
If heat flows from a system to its surroundings, the
enthalpy of the system decreases, so ΔHrxn is
negative.

Conversely, if heat flows from the surroundings to a

system, the enthalpy of the system increases,
is positive.
 Thus:
• ΔHrxn <0 for an exothermic reaction,
and
• ΔHrxn >0 for an endothermic reaction.
In chemical reactions, bond breaking requires an
input of energy and is therefore an endothermic
process, whereas bond making releases energy,
which is an exothermic process.

The sign conventions for heat flow and enthalpy

changes are summarized in the following table:
Reaction Type Q ΔHrxn

Exothermic <0 < 0 (heat flows from a

system to its
surroundings)

Endothermic >0 > 0 (heat flows from

the surroundings to a
system)
If ΔHrxn is negative, then the enthalpy of the
products is less than the enthalpy of the reactants;
that is, an exothermic reaction is energetically
downhill.
Conversely, if ΔHrxn is positive, then the enthalpy of
the products is greater than the enthalpy of the
reactants; thus, an endothermic reaction is
energetically uphill .

Two important characteristics of enthalpy and

changes in enthalpy are summarized in the following
discussion.
Bond breaking ALWAYS requires an input of energy;
bond making ALWAYS releases energy.

Reversing a reaction or a process changes the

sign of ΔH.
Ice absorbs heat when it melts (electrostatic
interactions are broken), so liquid water must
release heat when it freezes (electrostatic
interactions are formed):

heat+H2O(s)→H2O(l)ΔH>0
H2O(l)→H2O(s)+heatΔH<0
In both cases, the magnitude of the enthalpy change
is the same; only the sign is different.

For a clearer understanding of reaction, consider the

following application:
Problem no.1 How many joules are required to
heat 15.2 g of water at 35.0°C to 70.0°C?
In order to be able to determine how much heat is
required to increase the temperature of your sample
of water from 35.0∘C to 70.0∘C , you need to know
the value of water's specific heat.

As you know, a substance's specific heat tells you

how much heat is required to increase the
temperature of 1.0 g of that substance by 1∘C.
Water has a specific heat of about 4.18 J /g ∘C .
This tells you that in order to increase the
temperature of 1 g of water by 1∘C , you need to
provide it with 4.18 J of heat.

4.18 g of water by 1 ∘C , you would need 4.18 times

Therefore, in order to increase the temperature of

more heat than water's specific heat value.

Also, in order to increase the temperature of 4.18 g
of water by 4.18∘C , you will need (4.18×4.18) times
more heat than water's specific heat value.

The problem above wants you to increase 15.2

grams of water by 35.0∘C. This means that you will
be needing (15.2 x 35) times more heat than water’s
specific heat value
Mathematically, this is expressed as:
 q = (m)( c) ( ΔT)

where:
q is the heat absorbed
m is the mass of the sample
Lc is the specific heat of the substance
ΔT is the change in temperature (defined as final
temperature minus initial temperature

q = (15.2 g) (4.18 J/ g ∘C) (70.0-35.0) ∘C

Substitute the equation with the given values:

= 2,223.76 J
LESSON 3:ENTHALPHY
 WHAT IS ENTHALPY?
Enthalpy or enthalpy change, is how much
energy(in the form of heat) has been transferred
out or taken in during a chemical reaction.
Many compounds cannot be directly synthesized from
their elements.
In some cases, the reaction proceeds too slowly, or
side reactions produce substances other than the
desired compound.
In these cases, ΔH ͦ f (enthalpy change) can be
determined by an indirect approach, which is based
on Hess's law of heat summation, or simply Hess's
law.
HESS LAW

It is named after the Swiss chemist Germain Henri

Hess.
Hess's law is also known as "Hess's Law of
Constant Heat Summation." can be stated as:
"states that the total enthalpy of a chemical reaction is
the sum of the enthalpy changes for the steps of the
reaction".
HESS LAW

Therefore, you can find enthalpy change by breaking a

reaction into component steps that have known enthalpy
values.
HOW TO USE HESS'S LAW TO FIND THE ENTHALPY CHANGE OF A REACTION USING ENTHALPY DATA
FROM SIMILAR REACTIONS

Example Problem No. 1:

What is the value of AH for the following reaction?

2CO(g) + O2(g) → 2 CO2(g)(eq. 1)

Given:

2C(s) + O2(g) +2CO(g); ΔHf= -221.0 kJ/mol (eq. 2)

C(s) + O2(g) → CO2(g); ΔHf= -393.5 kJ/mol (eq. 3)

Solution:
Hess's Law says the total enthalpy change does not rely on the path taken from
beginning to end.
Enthalpy can be calculated in one grand step or multiple smaller steps.

Step 1: Manipulate given equations to most closely

resemble equation of interest.
To solve this type of problem, organize the given chemical reactions where the total
effect yields the reaction needed.
There are a few rules that you must follow when manipulating a reaction.
1. The reaction can be reversed. This will change the sign of ΔHf

2. The reaction can be multiplied by a constant. The value of ΔHf must be

multiplied by the same constant.

We see resemblance of value from the equation of interest (Eq. 1) to equation 2

2CO(g) + O2(g) → 2 CO2(g) (Eq. 1)

2C(s) + O2(g) →2CO(g); ΔHf= -221.0 kJ/mol (Eq. 2)

Flip equation 2 so that 2C0(g) will be on the reactant side
as reflected by the equation of interest. Applying rule #1,
this will become:

2CO(g) 2C(s) + O2(g) ; ΔHf= +221.0 kJ/mol (Eq

4)

Another resemblance from the equation of

interest (Eq. 1) to equation 3.

2CO(g)+ 02(g) 2 CO2(g) (Eq 1)

C(s) + O2(g) CO2(g); ΔHf = -393.5 kJ/mol (Eq. 3)

Both resemblance are on the product side but their coefficients are not
the same, therefore multiple the whole equation 3 to have a coefficient of
2. Applying rule #2, this will become:
2C(s) + 2O2(g) 2CO2(g); ΔHf= -707 kJ/mol (Eq. 5)

Step 2: Add new reactions together.

2CO(g)
Add 2C(s)4+and
equation O2(g) ; ΔHf= +221.0
equation kJ/mol (Eq
5 together 4 ) their ΔHf.This will become
with
2C(s) + 2O2(g) 2CO2(g) ; ΔHf= -787 kJ/mol (Eq. 5)

2CO(g) + 2C(s)+ 2O2(g) 2CO2(g) + 2C(s)+O2(g) ;ΔHf= -566 kJ/mol

 Step 3: Cancel out any compounds that are
the same on both sides of the reaction
arrow. Anything that are the some on both of the
reaction arrows can be cancelled out
2CO(g) 2C(s) + O2(g) ; ΔHf= +221.0 kJ/mol (Eq 4 )
2C(s) + 2O2(g) 2CO2(g) ; ΔHf= -787 kJ/mol (Eq. 5)

2CO(g) + 2C(s)+ 2O2(g) 2CO2(g) + 2C(s)+O2(g) ;ΔHf= -566 kJ/mol

Step 4: Write the new equation and double
check to make sure it matches the equation
of interest

2CO(g) + O2(g) 2CO2(g);ΔHf= -566 kJ/mol

Therefore the value of ΔHf for the following

reaction 2CO(g) + O2(g) 2CO2(g) is -566 kJ/mol.
THANK YOU :)