Chemistry for Engineers:

Thermochemistry is a branch of chemistry that qualitatively and quantitatively describes the energy changes that
occur during chemical reactions.

Nature of Energy

Energy is the capacity to do work.

Law of conservation of energy: Energy cannot be created or destroyed.Although energy can be converted
from one form to another, the total amount of energy in the universe remains constant

Energy, Heat, and Work

Mechanical work is the amount of energy required to move an object a given distance when opposed by a
force.

work = force x distance

w=Fd

Because the force (F) that opposes the action is equal to the mass (m) of the object times its acceleration (a), we can
also write the above Equation as follows:

work= mass x acceleration x distance

w=mad

Thermal energy is due to the random motions of atoms, molecules, or ions in a substance.

The temperature of an object is a measure of the amount of thermal energy it contains.

Heat (q) is the transfer of thermal energy from a hotter object to a cooler one. The net transfer of thermal
energy stops when the two objects reach the same temperature.

Kinetic and Potential Energy

Energy can take many forms; most are different varieties of potential energy (PE), energy caused by the
relative position or orientation of an object. Kinetic energy (KE) is the energy an object possesses due to its
motion.

1
KE  mv2
2

For example, the kinetic energy of a 1360 kg (approximately 3000 lb) automobile traveling at a velocity of 26.8 m/s
(approximately 60 mi/h) is

KE=1/2(1360kg)(26.8m/s)2=4.88×105 kg.m2/s2

Also, calculate the potential energy of the same 1360 kg automobile if it were parked on the top level of a parking
garage 36.6 m (120 ft) high. Its potential energy is equivalent to the amount of work required to raise the vehicle
from street level to the top level of the parking garage, which is w = Fd

PE=Fd=mad=mgh

PE=(1360,Kg)(9.81m/s2)(36.6m)=4.88×105 kg.m2/s2

=4.88×105J=488kJ

The units of potential energy are the same as the units of kinetic energy. Notice that in this case the potential energy
of the stationary automobile at the top of a 36.6 m high parking garage is the same as its kinetic energy at 60 mi/h.

Example:

a. If the mass of a baseball is 149 g, what is the kinetic energy of a fastball clocked at 100 mi/h?1.49×102J
b. A batter hits a pop fly, and the baseball (with a mass of 149 g) reaches an altitude of 250 ft. If we assume that
the ball was 3 ft above home plate when hit by the batter, what is the increase in its potential
energy?1.10×102J
The most common units of energy are the joule (J), defined as 1 (kg·m2)/s2, and the calorie, defined as the
amount of energy needed to raise the temperature of 1 g of water by 1°C (1 cal = 4.184 J).

The First Law of Thermodynamics

The system is that part of the universe we are interested in studying, such as a chemical reaction inside a flask. The
surroundings are the rest of the universe, including the container in which the reaction is carried out.

1.Open systems can exchange both matter and energy with their surroundings

2.Closed systems can exchange energy but not matter with their surroundings, and

3. Isolated systems can exchange neither matter nor energy with their surroundings.

A truly isolated system does not actually exist. An insulated thermos containing hot coffee approximates an isolated
system, but eventually the coffee cools as heat is transferred to the surroundings. In all cases, the amount of heat lost
by a system is equal to the amount of heat gained by its surroundings and vice versa

A state function is a property of a system that depends on only its present state, not its history.

A state function is a property of a system whose magnitude depends on only the present state of the system, not its
previous history. Temperature, pressure, volume, and potential energy are all state functions. The temperature of an
oven, for example, is independent of however many steps it may have taken for it to reach that temperature. Similarly,
the pressure in a tire is independent of how often air is pumped into the tire for it to reach that pressure, as is the final
volume of air in the tire. Heat and work, on the other hand, are not state functions because they are path dependent.

Direction of Heat Flow

A reaction or process in which heat is transferred from a system to its surroundings is exothermic. A reaction or
process in which heat is transferred to a system from its surroundings is endothermic.

The First Law

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. When the volume of a system is constant, changes in its internal
energy can be calculated by substituting the ideal gas law into the equation for ΔU.

The relationship between the energy change of a system and that of its surroundings is given by the first law of
thermodynamics, which states that the energy of the universe is constant. We can express this law mathematically
as follows:

Uuniv = ΔUsys + ΔUsurr =0

ΔUsys = − ΔUsurr

The tendency of all systems, chemical or otherwise, is to move toward the state with the lowest possible energy.

Because heat and work are the only two ways in which energy can be transferred between a system and its
surroundings, any change in the internal energy of the system is the sum of the heat transferred (q) and the work
done (w):

ΔUsys = q + w
Although qq and ww are not state functions on their own, their sum (ΔUsys ) is independent of the path taken and is
therefore a state function.

Thus, because of the first law, we can determine ΔUΔU for any process if we can measure both qq and ww . Heat, qq ,
may be calculated by measuring a change in temperature of the surroundings. Work, ww , may come in different
forms, but it too can be measured. One important form of work for chemistry is pressure-volume work done by an
expanding gas. At a constant external pressure (for example, atmospheric pressure)

w=−PΔV

The negative sign associated with PV work done indicates that the system loses energy when the volume increases.
That is, an expanding gas does work on its surroundings, while a gas that is compressed has work done on it by the
surroundings.

Example1:

A sample of an ideal gas in the cylinder of an engine is compressed from 400 mL to 50.0 mL during the compression
stroke against a constant pressure of 8.00 atm. At the same time, 140 J of energy is transferred from the gas to the
surroundings as heat. What is the total change in the internal energy (ΔU) of the gas in joules?w=284J; ΔU=144 J

Example2:

A sample of an ideal gas is allowed to expand from an initial volume of 0.200 L to a final volume of 3.50 L against a
constant external pressure of 0.995 atm. At the same time, 117 J of heat is transferred from the surroundings to the
gas. What is the total change in the internal energy (ΔU) of the gas in joules?W= -332.7 J;ΔU= -216 J

Enthalpy
Work, like heat, exists only when energy is being transferred. When two bodies are placed in thermal contact and
energy flows from the warmer body to the cooler one, this process is called “heat”. A transfer of energy to or from a
system by any means other than heat is called “work”.

Enthalpy as a Composite Function

Enthalpy is a state function, and the change in enthalpy of a system is equal to the sum of the change in the internal
energy of the system and the PV work done. Enthalpy is a state function whose change indicates the amount of heat
transferred from a system to its surroundings or vice versa, at constant pressure.

To further understand the relationship between heat flow (q) and the resulting change in internal energy (ΔU ), we
can look at two sets of limiting conditions: reactions that occur at constant volume and reactions that occur at
constant pressure.

ΔU = q − P ΔV

If the reaction occurs in a closed vessel, the volume of the system is fixed, and ΔV is zero. Under these conditions, the
heat flow (often given the symbol qv to indicate constant volume) must equal ΔU:

For constant volume,

qv =ΔU

For constant pressure,

Qp = ΔU + PΔV
Thus, at constant pressure, the heat flow for any process is equal to the change in the internal energy of the system
plus the PV work done.

Because conditions of constant pressure are so important in chemistry, a new state function called enthalpy (H) is
defined as

H =U +PV

At constant pressure, the change in the enthalpy of a system is as follows:

ΔH= ΔU + Δ(PV )=ΔU + PΔV

Comparing the previous two equations shows that at constant pressure, the change in the enthalpy of a system is
equal to the heat flow: ΔH=qpΔH=qp . This expression is consistent with our definition of enthalpy, where we stated
that enthalpy is the heat absorbed or produced during any process that occurs at constant pressure.

Example 1: The molar enthalpy of fusion for ice at 0.0°C and a pressure of 1.00 atm is 6.01 kJ, and the molar
volumes of ice and water at 0°C are 0.0197 L and 0.0180 L, respectively. Calculate ΔH and ΔU for the melting of ice
at 0.0°C. ΔU=6010.17 J

Example 2: At 298 K and 1 atm, the conversion of graphite to diamond requires the input of 1.850 kJ of heat per
mole of carbon. The molar volumes of graphite and diamond are 0.00534 L and 0.00342 L, respectively. Calculate ΔH
and ΔU for the conversion of C (graphite) to C (diamond) under these conditions. ΔU=1.85 kJ/mol

The Relationship between ΔH and ΔU

If gases are involved,

PV = nRT

Recognizing that Δ(PV) = Δ(nRT), we can rewrite

ΔH = ΔU + Δ(PV ) = ΔU + Δ(n RT)

At constant temperature, Δ(nRT) = RTΔn, where Δn is the difference between the final and initial numbers of moles
of gas. Thus

ΔU= ΔH − RT Δn

Δn= no. Of moles of product gas/gases- no. Of moles reactant gas/gases

For reactions that result in a net production of gas, Δn > 0, so ΔU < ΔH. Conversely, endothermic reactions (ΔH > 0)
that result in a net consumption of gas have Δn < 0 and ΔU > ΔH.

Example 1: The Relationship Between ΔH and ΔU in Gas Evolving Reactions

The combustion of graphite to produce carbon dioxide is described by the equation

At 298 K and 1.0 atm, ΔH = −393.5 kJ/mol of graphite for this reaction, and the molar volume of graphite is 0.0053
L. What is ΔU for the reaction?

To understand why only the change in the volume of the gases needs to be considered, notice that the molar volume
of graphite is only 0.0053 L. A change in the number of moles of gas corresponds to a volume change of 22.4 L/mol
of gas at standard temperature and pressure (STP), so the volume of gas consumed or produced in this case is
(1)(22.4 L) = 22.4 L, which is much, much greater than the volume of 1 mol of a solid such as graphite.

Exercise 2: Calculate ΔU for the conversion of oxygen gas to ozone at 298 K:

3O2(g) → 2O3 (g)

The value of ΔH for the reaction is 285.4 kJ. ΔH= 288 KJ