The First Law of Thermodynamics

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 What is Thermodynamics?
• Thermodynamics is a branch of physics that deals with heat, work, and temperature, and their
relation to energy, entropy, and the physical properties of matter and radiation. The behavior of
these quantities is governed by the four laws of thermodynamics which convey a quantitative
description using measurable macroscopic physical quantities, but may be explained in terms
of microscopic constituents by statistical mechanics. Thermodynamics applies to a wide
variety of topics in science and engineering, especially physical chemistry, biochemistry, 
chemical engineering and mechanical engineering, but also in other complex fields such as 
meteorology.
What is Chemical Thermodynamics?
Chemical thermodynamics is the study of the interrelation of heat and 
work with chemical reactions or with physical changes of state within
the confines of the laws of thermodynamics. Chemical thermodynamics
involves not only laboratory measurements of various thermodynamic
properties, but also the application of mathematical methods to the
study of chemical questions and the spontaneity of processes.
Basic Terminology
System
A thermodynamic system is a body of matter and/or radiation, confined in space by walls, with
defined permeabilities, which separate it from its surroundings. The surroundings may include
other thermodynamic systems, or physical systems that are not thermodynamic systems .

Surrounding
The surroundings contain everything other than the system. The system and the surroundings
together make up the universe. A thermodynamic system is embedded in its environment or
surroundings, through which it can exchange heat with, and do work on. It exchanges the heat
to its surroundings through a boundary.
Delta(∆)
uppercase delta (Δ) at most times means “change” or “the change” in maths. Consider an
example, in which a variable x stands for the movement of an object. So, “Δx” means “the
change in movement.” Scientists make use of this mathematical meaning of delta in various
branches of science.
Joules(J)
Joule heating is the physical effect by which the pass of current through an electrical
conductor produces thermal energy. This thermal energy is then evidenced through a rise
in the conductor material temperature, thus the term “heating”.
What is the first law of
thermodynamics?
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
Law of Conservation of
Energy
The law of conservation of
energy states that energy can
neither be created nor destroyed -
only converted from one form of
energy to another. This means
that a system always has the
same amount of energy, unless
it's added from the outside.
Examples
Figures in the right shows two examples of
energy being transferred from one system to
another and from one form to another.
Humans can convert the chemical energy in
food like the ice cream cone into kinetic
energy(the energy of movement to ride a
bicycle. Plants can convert light energy from
the sun into chemical energy
Examples
Light bulbs transform electrical energy into
light energy (radiant energy).
One pool ball hits another, transferring
kinetic energy and making the second ball
move.
Plants convert the energy of sunlight (radiant
energy) into chemical energy stored in
organic molecules.
You are transforming chemical energy from
your last snack into kinetic energy as you
walk, breathe, and move your finger to scroll
up and down this page.
• How are these quantities related when we speak of thermodynamic
systems? In this Law, the energy added to a system is equal to the sum of
increase in internal energy and the external work done by the system.
Heat Input= Increase in Internal Energy + Work Output
∆U = q + w
Where:
∆U=total change of internal energy in a system
q- the heat exchanged between a system and its surroundings
W- work is done by a system
• The First Law of Thermodynamics or Law of conservation of energy
states that energy can be converted from one form to another with the
interaction of heat, work and internal energy, but it cannot be created
nor destroyed, under any circumstances.
• The first law of thermodynamics defines the internal energy (E) as
equal to the sum of the heat transfer (Q) into a system and the work
(W) done by the system.
• ΔU or ∆E is the total change in internal energy of a system,• q is the
heat exchanged between a system and its surroundings, and• w is the
work done by or on the system.
• This means that if energy is input to a system by doing work on it,
then it will get hotter. If the system is to stay the same temperature,
then you must remove heat from the system - .
• The first law of thermodynamics is a generalization of the law of
conservation of energy, which states that energy can neither be created
nor destroyed.[
• This is a particularly important law when discussing heat engines (like car
engines), because it helps to understand that heat must go somewhere—the
basis for cogeneration. As an engine creates heat, if the heat is not vented,
the engine will become hotter and hotter, which will eventually lead to
melting. Therefore, because it is impossible to achieve 100% efficiency
(see carnot efficiency), heat must be vented. This can either be treated as
waste heat, or used for cogeneration, which is applying the waste heat to
another cause, like heating a car, or heating houses.
 Heat
• Heat is the energy transferred due to the temperature difference
between the system and the surrounding area. On heating, the
kinetic energy of the molecules increases and therefore the
internal energy increases.
• Heat is the transfer of kinetic energy from one medium or object
to another, or from an energy source to a medium or object. Such
energy transfer can occur in three ways: radiation, conduction,
and convection.
• In thermodynamics, heat is defined as the form of energy crossing
the boundary of a thermodynamic system by virtue of a
temperature difference across the boundary.
Work
• In thermodynamics, work is one of the principal processes by which a
thermodynamic system can interact with its surroundings and
exchange energy. An exchange of energy is facilitated by a mechanism
through which the system can spontaneously exert macroscopic forces
on its surroundings, or vice versa
• In thermodynamics, thermodynamic work is the quantity of energy
transferred from one system to another. It is a generalization of the
concept of mechanical work in mechanics. In the SI system of
measurement, work is measured in joules (symbol: J). The rate at
which work is performed is power.
Internal Energy
• One of the thermodynamic properties of a system is its internal energy, E or
U, which is the sum of the kinetic and potential energies of the particles that
form the system. The internal energy of a system can be understood by
examining the simplest possible system: an ideal gas.
• Examples of internal energy are the temperature and state of a substance. For
example the internal energy of water depends on whether it is in the solid,
liquid or gas state and it's temperature. Liquid water has more internal
energy than solid copper at the same temperature due to its state
• The first law of thermodynamics states that the energy of the universe is
constant. The change in the internal energy of a system is the sum of the heat
transferred and the work done. The heat flow is equal to the change in the
internal energy of the system plus the PV work done.
The First Law of
Thermodynamics
If the heat flows into the system it gains energy the
surrounding do the work in the system internal
energy 2 ways a system heats and increase in
energy
∆U= + 300( energy by the system grows up by 300)
∆U= - 300( energy in the surrounding decrease by
300)
∆U of the system while the ∆U of the surrounding
decreases
So energy is not created or destroyed it is simply
transferred from one place to another.
The system didn't get just the 300 joules from
somewhere it came from the surroundings .
If the system gained 300 joules of energy the. The
surrounding loses 300 joules of energy. If the system
loses 300 joules of energy then the surroundings
gains 300 joules of energy
3 Types of System
• What is a System?
A thermodynamic system is defined as a quantity of matter or a
region in space that is of interest. The mass or region outside the
system is called the surroundings, and the surface that separates the
system and the surroundings is called the boundary.
3 types
1. Open System
2. Close System
3. Isolated System
Isolated System
An isolated system is one that
cannot exchange either matter or
energy with its surroundings. A
perfect isolated system is hard to
come by, but an insulated drink
cooler with a lid is conceptually
similar to a true isolated system.
Closed System
A closed system is that in which only the exchange
of energy is allowed but the exchange of matter is
not allowed. Example-When we boil water with a
closed lid, the heat can exchange but matter cannot.
Open System
An open system can exchange both
energy and matter with its
surroundings. The stovetop example
would be an open system, because heat
and water vapor can be lost to the air. A
closed system, on the other hand, can
exchange only energy with its
surroundings, not matter.
Thermal Chemistry: The First Law of
Thermodynamics
The First law of Thermodynamics
• Popularly known as the law of energy conservation
• Outlines the relationship
Internal energy= U
Work= W
Heat= Q
∆U= Q+W
Means change in internal energy of the system will be equal to the energy
transferred to or from the system as heat added energy transferred to or from the
system As work/ done on or by the system.
All quantity is measured by joules
Scenarios
1. Constant Volume (w=0)  isovolumetric.
∆U= Q - W
∆U= Q - O
∆U= Q
• Any change in internal energy must be the result of heat transfer in or out
• Isovolumetric process means no change in volume
Example: Bomb Calorimeter
Where a combustion occurs in a rigid container such that only heat transfer occurs.

2. Constant Volume(∆U= 0) isothermal

∆U= Q – W
∆U= Q – w
Q= W
• any heat transferred is completely used for work
• isothermal process means no change in the temparature
Example: ideal version of a car engine
. Would be use all its energy for work
3.) No heat transfer (Q=0)  adiabatic
∆U = Q – W
∆U = 0 – W
∆U = -W
• Internal energy is used exclusively for work
• Adiabatic process means no heat transfer
Example: Certain processes in Earth’s atmosphere
as masses of air change position due to pressure difference
4.) Q = 0 and W = 0  isolated system
∆U = Q –W
∆U = 0 – 0
∆U = 0
• No change in internal energy
The law thermodynamics chemistry vs
physics
Chemistry Physics
• ∆U= q + w • ∆U= q - w

Q = heat energy Q= heat energy

W= work W= work

In chemistry we take the In physics we take the viewpoint

systems point of view of the surroundings
Physics
W= - negative anytime work is done by the system the system has to
expand energy do work so internal energy of the system decreases
In physics takes the viewpoint of the surrounding
Chemistry
W= + positive when work is done on the system
In chemistry we take the viewpoint of the system
 q=is + positive when the system absorbed heat energy
Everytime heat energy flows into the system heat energy is
absorbed by the system so q is positive.
It is called Endothermic process
q= is – negative when the system releases heat energy
So energy flow out of the system out to the surrounding
It is called Exothermic Process
Q= –}Because heat is exert or release out of the system. It is called
exothermic process
System q= - } q relative to the system
Q= is measured by joules
Things needed to take note:
The unit of conversion
1 kj= 1000J
1 cal= 4.184J
1 cal= 1000Cal
Formulas
Equation for internal energy
∆U= q + w
Equation for work
W= –P ∆ V
Equation for the energy that leaves and enters the system
q= mc ∆ t
For Phase change
Q= m ∆ h Or Q= n ∆ h
Conversion is the recommended process
Enthalpy reaction using heat of formation
∆ Hrxn°= Products – Reactants
Hess’ Law
FORMULA AND SOLVING
1.) How much energy is transferred as heat if 100 J of work is done on a system and
internal energy increases by 74 J?

Given: W = 100 J
∆U = 74 J
Required: Q = ?
Solution: ∆U = Q + W
Q = ∆U + W
Q = 74 J + (-100 J)
Q = - 26 J
• Heat lost in the process.
SOLVING AND FORMULA
2.) A sample of gas does 150 J of work against its surroundings and loses 90 J of internal
energy in the process. Does the gas gain or lose heat, and how much?

Given: W = 150 J
∆U = -90 J
Required: Q = ?
Solution: ∆U = Q + W
Q = ∆U + W
Q = (-90 J) + (150 J)
Q = 60 J
• 60 J of heat are absorbed for this to occur.
Solving
A container has a sample of nitrogen gas and a tightly movable piston that’s
not allow any gas to escape. During a thermodynamic process 200 joules of
heat enter the gas and the gas does 300 joules of work in the process?
Given: q = 200 J
q = 300 J
Required: ∆U
Equation: ∆U = q + w
Solution:∆U = (+200 J ) + (–300 J )
Final Answer: ∆U= -100 J
For work
W= –P ∆ V
W= work
P= pressure
V= volume
“When work is done on the system it is positve” w=+
“ When work is done by the system it is negative” w= –
When the change of volume is positive(+)
∆V= + the work is negative ( w= –)
When the change of volume is negative
∆V= –the work is positive (w= +)
Unit of convertion
101.3 joules or J= 1 L. atm
Problem:
If 300 joules of heat energy was absorbed by the system, the gas expanded from 2L 3
L 5 atm. Calculate the work and the internal energy.
Given: P= 5 atm
2 L and 3 L
300J
Required: work and internal energy
Equation: W= –P ∆ V
∆U= q + w
Solution: W= –P ∆ V
W= -5atm( 3L – 2L)
= -5L-atm
To get W convert Liters times atm into joules
( 𝑥+𝑎 )𝑛 =¿
For heat
Formula
Q= mc∆T
M= mass
C= specific heat capacity
∆T= change in temperature which can be in Kelvin or Celsius
Unit of Conversion
1 heat capacity of water(H2O) = 4.184 J/g °C
Sample Equation
How much heat energy is absorbed by 50 grams of water if the temperature rises from 25°c to 75
°c( the specifuc heat capacity of water is 4.184 J/gc
50g 25°C  75° C
75
–25
–––––
50°C
Q= 50(4.184) (50°)
Q= 10,460J} the amount of heat energy required to heat up 50 grams of water from 25 degrees Celsius
to 75° degrees Celsius.
If you want to convert to kilojoules
Kj= 10,460
––––––– = 10.56 Kj
1000
Calculation of the amount of energy absorbed or release
whenever there's a temperature change.
The equation is
Q= m c ∆ T
For phase change
Whenever you want to calculate the amount of heat energy that absurd or release
whenever there us a phase change.
Formula Could be
Q=m∆H enthalpy of
fusion or
Q=n∆H vaporization

But the process we will use is conversion

Example:
54 grams of ice at 0° Celsius
Required: how much heat energy is Absorbed in order to melt that ice into liquid water.
While use is melting to liquid water to temperature remains constant
Phase change which goes from solid into liquid
We must know first the heat of fusion of water
∆H fus= 6kg/mol} means if 1 mol of H2O is equal to required 6 kilojoules melt of ice
Find the molar mass
H = 2 x 1= 2
O= 15.99903
–––––––––
17.99903 grams of H2O
Conversion process
g  mol  kj
Thermal Chemical Equation for Combustion Reaction
C3H8+O2 CO2 + H20}these reaction +1200 kj of energy
Balance the equation
C=3 C=1
H=8 H=2
O=2 O=3
1C3H8+5O23CO2+4H2O
C= 3 C=1=3
H=8 H=2=8
O=2 O=3=10

C=3 C=3
H=8 H=8
O=10 O=10
How many kilojoules
Hess’s Law
• It uses the enthalpy values of other to predict the enthalpy change
for a different reaction.
• Hess’s Law of Constant Heat Summation (or just Hess’s Law) states
that regardless of multiple stages or steps of a reaction, the total
enthalpy change for the reaction is the sum of all changes. This law
is a manifestation that enthalpy is a state function.
• Hess’s Law: the heat of any reaction Hf for a specific reaction is
equal to the sum of the heats of reaction for any set of reactions
which in sum are equivalent to the overall reaction.
Hess’s Law
• 1. A + B C 100J
• 2. C+D E 200J
• 3.A+B+D E H=300J

• According to Hess’s Law since we add the equation 1and 2 to get

equation 3 the enthalpy changes of the equation 1 and 2.
HESS’S LAW
SAMPLE EQUATION
1. 2H2O 2H2 +O2 +572J
2. 2HF H2+O2(x2R) +542J
2F2+2H2O 4HF +O2
MODIFIED:
2H2O 2H2+O2 572J
2H2 +2F2 4HF -1084J
2H2O+ 2F2 O2+4HF -512J
• 2NH3 N2 +3NH2 (x2) +92J
• 2H2O 2H2+ O2 (x3R) +572J
• N2+O2 2NO(x2) -180J
4NH3 +5O2 4NO +6H2O
MODIFIED:
4NH3 2N2+6N2 +184J
6H2+3O2 6H2O -1716J
2N2+2O2 4NO -360J

4NH3+5O2 4NO +6H2O 1892J

The relationship of hess’ law to the first law
of thermodynamics
Hess's law is based on the first law of thermodynamics which says
that energy cannot be created or destroyed but can be converted from
one form to another. Hess's Law of Heat Summation states that the
enthalpy change for a reaction is the same whether it occurs by one step
or by any (hypothetical) series of steps.
Enthalpy of combustion using heat of
formation
the standard heat of formation of CH4 Is -76.2, CO2 -398.8 and H2O is – 241.6.
calculate the standard enthalpy of combustion.
CH4 + O2  CO2 + 2H20
BALANCE
1CH4+ 2O2 1CO2 + 2H2O

∆H°rxn=∑(PRODUCT) - ∑(REACTANTS)
=(1CO2 + 2H2O) – (1CH4+ 2O2)
=[-398.8 – 2(241.6)] – [ -76.2+0]
= - 398.8 – 483.2+ 76.2
= -800 kj/mol
enthalpy of combustion using heat of
formation
If the heat of formation of CH4 is -785 , CO2 -393, H2O is -286 kj mol respectively. Calculate the
enthalpy of combustion.

CH4 + O2 CO2 + 2H2O

Reactant}1CH4 + 2O2 1CO2 + 2H2O } products
-785 -393 -286
C= 1 C=1
H=4 H=4
O=2+2=4 O=4
BALANCE EQUATION
C= 1 C=1
H=4 H=4
O=4 O=4

∆Hrxn◦=∑(PRODUCT) - ∑(REACTANTS)
∆Hrxn◦=[CO2 + 2H2 5O] – [1CH4 + 2O2]
∆Hrxn◦=[ -393 + 2(-286)] – [ -785 + 0]
∆Hrxn◦= -393+ 576 + 785
∆Hrxn◦= -184 } enthalpy of reaction using heat of formation