Laws of Thermodynamics

Thermodynamics

• Thermodynamics is the study of the effects of work, heat, and energy on a system

• Thermodynamics is only concerned with macroscopic (large-scale) changes and observations

• All of thermodynamics can be expressed in terms of four quantities

• Temperature (T)

• Internal Energy (U)

• Entropy (S)

• Heat (Q)

• These quantities will be defined as we progress through the lesson

CLASSICAL VERSUS STATISTICAL

• Classical thermodynamics concerns the relationships between bulk properties of matter. Nothing is examined at
the atomic or molecular level.

• Statistical thermodynamics seeks to explain those bulk properties in terms of constituent atoms. The statistical
part treats the aggregation of atoms, not the behavior of any individual atom

According to British scientist C. P. Snow, the three laws of thermodynamics can be (humorously)
summarized as

• 1. You can’t win

• 2. You can’t even break even

• 3. You can’t get out of the game

4.0 The Zeroth Law

• The First and Second Laws were well entrenched when an additional
Law was recognized (couldn’t renumber the 1 st and 2nd Laws)

• If objects A and B are each in thermal equilibrium with object C, then A

and B are in thermal equilibrium with each other

• Allows us to define temperature relative to an established standard

 •

The First Law of Thermodynamics

The first law of thermodynamics is a statement of the conservation of energy.

If a system’s volume is constant, and heat is added, its internal energy increases.

If a system does work on the external world, and no heat is added, its internal energy decreases.
 1.0 You can’t win (1st law)

• The first law of thermodynamics is an extension of the law of conservation of energy

• The change in internal energy of a system is equal to the heat added to the system minus the work done by the
system

ΔU = Q – W

Combining these gives the first law of thermodynamics. The change in a system’s internal energy is related to the heat Q
and the work W as follows:

It is vital to keep track of the signs of Q and W.

The internal energy of the system depends only on its temperature. The work
done and the heat added, however, depend on the details of the process
involved.

Thermal Processes
We will assume that all processes we discuss
are quasi-static – they are slow enough that
the system is always in equilibrium.

We also assume they are reversible:

For a process to be reversible, it must be

possible to return both the system and its
surroundings to exactly the same states they
were in before the process began.
This is an idealized reversible process. The gas is compressed; the temperature is constant, so heat leaves the gas. As
the gas expands, it draws heat from the reservoir, returning the gas and the reservoir to their initial states. The piston
is assumed frictionless.

Thermal Process Terminology

• Adiabatic – no heat transferred

• Isothermal – constant temperature

• Isobaric – constant pressure

• Isochoric – constant volume

Adiabatic Process

• An adiabatic process transfers no heat

– therefore Q = 0

• ΔU = Q – W

• When a system expands adiabatically, W is positive (the system does work) so ΔU is negative.

• When a system compresses adiabatically, W is negative (work is done on the system) so ΔU is positive.

• An adiabatic process is one in which no heat flows into or out of the system. The adiabatic P-V curve is similar to
the isothermal one, but is steeper. One way to ensure that a process is adiabatic is to insulate the system.

•
 • Another way to ensure that a process is effectively adiabatic is to have the
volume change occur very quickly. In this case, heat has no time to flow in or
out of the system.

Isothermal Process

• An isothermal process is a constant temperature process. Any heat flow into

or out of the system must be slow enough to maintain thermal equilibrium

• For ideal gases, if ΔT is zero, ΔU = 0

• Therefore, Q = W

– Any energy entering the system (Q) must leave as work (W)

Isothermal Processes

If the temperature is constant, the pressure varies inversely with the

volume.

The work done is the area under the curve:

Isobaric Process

• An isobaric process is a constant pressure process. ΔU, W, and Q are generally non-zero, but calculating the
work done by an ideal gas is straightforward

W = P·ΔV

• Water boiling in a saucepan is an example of an isobar process

• Work done by an expanding gas, constant

pressure:
 Isochoric Process

• An isochoric process is a constant volume process. When the volume of a system doesn’t change, it will do no
work on its surroundings. W = 0

ΔU = Q

• Heating gas in a closed container is an isochoric process

• If the volume stays constant, nothing moves and no work is done.

Here is a summary of the different types of thermal processes:

Heat Capacity

• The amount of heat required to raise a certain mass of a material by a certain temperature is called heat
capacity

Q = mcxΔT

• The constant cx is called the specific heat of substance x, (SI units of J/kg·K)

• Specific Heats for an Ideal Gas: Constant Pressure, Constant Volume

• Specific heats for ideal gases must be quoted either at constant pressure or at constant volume. For a
constant-volume process,

• At constant pressure,

•
 • Both CV and CP can be calculated for a monatomic ideal gas using the first law of thermodynamics.

• Although this calculation was done for an ideal, monatomic gas, it works well for real gases.

The P-V curve for an adiabatic is given by

Heat Capacity of Ideal Gas

• CV = heat capacity at constant volume

CV = 3/2 R

• CP = heat capacity at constant pressure

CP = 5/2 R

• For constant volume

]Q = nCVΔT = ΔU

• The universal gas constant R = 8.314 J/mol·K

 Acids, Bases, and the pH scale
• Acids

• pH of 0 - <7

• React with metals and Bases

• Tend to taste sour

• Give off/ contribute H+ ions into a solution

• Ex.) HCl  H+(aq) + Cl-(aq)

• (aq) stands for aqueous, which means it is a solution in which the solvent is water (dissolved in water)

• There is a very strong acid in our stomach, HCl. This is what sometimes cause heartburn.

• Bases

• pH of >7 - 14

• Do not react with metals

• React with acids

• Tend to taste bitter

• Give off/ contribute hydroxide ions ( OH- )to a solution

• ex.) NaOH  Na+(aq) + OH-(aq)

NEUTRAL

• pH of 7

• Neither acidic nor basic

• Pure water

NEUTRALIZATION

• We can neutralize an acid with a base, or neutralize a base with an acid.

• Ex.) There are bases secreted in our intestines that neutralize the acid from our stomach.

The pH Scale

 A scale developed in order to determine how acidic or basic a substance is.

 Values on the scale range from 0-14.

INDICATOR

 A substance that changes color in the presence of an acid or base.

 Ex. Cabbage Juice, litmus paper

pH reader
ACIDS

Substances that donate hydrogen ions, H+, to form hydronium ions, H3O+, when dissolved in water

Formation of Hydronium Ions A. Characteristics of acids

1. Acids turn blue litmus paper red

 Litmus paper is an indicator

2. Acids taste sour

3. Can burn skin

Common Acids

Sulfuric Acid H2SO4 BATTERY ACID

Nitric Acid HNO3 Used to make fertilizers and explosives

Phosphoric Acid H3PO4 Food flavoring

Hydrochloric Acid HCl Stomach acid

Acetic Acid CH3COOH Vinegar

Carbonic Acid H2CO3 Carbonated water

B. Strong vs. Weak acids

1. Strong acids – ionize (break in to cations and anions) almost completely, and conduct electricity well

a. Nitric acid (HNO3)

b. Hydrochloric acid (HCl)

c. Sulfuric acid (H2SO4)

d. Perchloric acid

2. Weak acids – do not completely ionize

a. Acetic acid (vinegar)

b. Citric acid

c. ALL others

II. What are bases?

- Substances that form hydroxide ions (OH -) ions when in water, or accept H+ ions

A. Characteristics of Bases
B. 1. Taste bitter
C. 2. Slippery
D. 3. Bases turn red
E. litmus paper blue
F. 4. Can burn skin
B. Strong vs. Weak bases
1. Strong bases - ionize (break into cations and anions) almost completely, and conduct electricity well
a. KOH – potassium hydroxide
b. NaOH – sodium hydroxide
 2. Weak bases - do not completely ionize
a. Ammonia (NH3)

 Acid: A solution that has an excess of H+ ions. It comes from the Latin word acidus that means "sharp" or "sour".
 Base: A solution that has an excess of OH- ions. Another word for base is alkali.
 Aqueous: A solution that is mainly water. Think about the word aquarium. AQUA means water.
III. Why is a substance neutral?
 A substance is neutral when:
1. It does not ionize at all, therefore no
H+ or OH- ions
2. It has equal concentrations
(amounts) of H+ and OH- ions
IV. How acidic or basic is it?

Concentration vs. Strength

 Concentration is not the same as strength
 Concentration deals with the amount of hydronium ions in the solution, compared to the amount of water in the
solution.
 More acid or base and less water
= more concentrated
 More ions and less molecules
= stronger
III. How acidic or basic is it?
C. pH scale  0-14
 Indicates concentration of hydronium ions
0-6 = acid  closer to 0 is more acidic

8-14 = base  closer to 14 is more basic

7 = neutral  H3O+ concentration = OH- concentrations

D. Each pH unit = a power of ten

- Example: pH 3 is 100 times more acidic than pH 5
 Strong Acid: An acid that has a very low pH (0-4).
 Strong Base: A base that has a very high pH (10-14).
 Weak Acid: An acid that only partially ionizes in an aqueous solution. That means not every molecule breaks
apart. They usually have a pH close to 7 (3-6).
 Weak Base: A base that only partially ionizes in an aqueous solution. That means not every molecule breaks
apart. They usually have a pH close to 7 (8-10).
 Neutral: A solution that has a pH of 7. It is neither acidic nor basic.