KWAME NKRUMAH UNIVERSITY OF SCIENCE AND TECHNOLOGY (KNUST),

KUMASI

COLLEGE OF SCIENCE

FACULTY OF COMPUTATIONAL AND PHYSICAL SCIENCES

DEPARTMENT OF PHYSICS

TITLE: HOW THERMODYNAMICS IS APPLIED AT A BREWING COMPANY

AGBOVE OPPONG HENRY 4652618

DATE:23rd NOVEMBER,2019
INTRODUCTION

Thermodynamics is the branch of physics that deals with heat and temperature, and their relation to
energy, work, radiation, and properties of matter. 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, chemical engineering and mechanical engineering, but also in fields as complex as
meteorology.

Historically, thermodynamics developed out of a desire to increase the efficiency of early steam engines,
particularly through the work of French physicist Nicolas Léonard Sadi Carnot (1824) who believed that
engine efficiency was the key that could help France win the Napoleonic Wars.[1] Scots-Irish physicist
Lord Kelvin was the first to formulate a concise definition of thermodynamics in 1854[2] which stated,
"Thermo-dynamics is the subject of the relation of heat to forces acting between contiguous parts of
bodies, and the relation of heat to electrical agency."

The initial application of thermodynamics to mechanical heat engines was quickly extended to the study
of chemical compounds and chemical reactions. Chemical thermodynamics studies the nature of the role
of entropy in the process of chemical reactions and has provided the bulk of expansion and knowledge of
the field. Other formulations of thermodynamics emerged. Statistical thermodynamics, or statistical
mechanics, concerns itself with statistical predictions of the collective motion of particles from their
microscopic behavior. In 1909, Constantin Carathéodory presented a purely mathematical approach in an
axiomatic formulation, a description often referred to as geometrical thermodynamics.

LAWS OF THERMODYNAMICS

Thermodynamics is principally based on a set of four laws which are universally valid when applied to
systems that fall within the constraints implied by each. In the various theoretical descriptions of
thermodynamics these laws may be expressed in seemingly differing forms, but the most prominent
formulations are the following.

Zeroth Law

The zeroth law of thermodynamics states: If two systems are each in thermal equilibrium with a third,
they are also in thermal equilibrium with each other.

This statement implies that thermal equilibrium is an equivalence relation on the set of thermodynamic
systems under consideration. Systems are said to be in equilibrium if the small, random exchanges
between them (e.g. Brownian motion) do not lead to a net change in energy. This law is tacitly assumed in
every measurement of temperature. Thus, if one seeks to decide whether two bodies are at the same
temperature, it is not necessary to bring them into contact and measure any changes of their observable
properties in time. The law provides an empirical definition of temperature, and justification for the
construction of practical thermometers.
The zeroth law was not initially recognized as a separate law of thermodynamics, as its basis in
thermodynamical equilibrium was implied in the other laws. The first, second, and third laws had been
explicitly stated already, and found common acceptance in the physics community before the importance
of the zeroth law for the definition of temperature was realized. As it was impractical to renumber the
other laws, it was named the zeroth law.

First Law

The first law of thermodynamics states: In a process without transfer of matter, the change in internal
energy, ΔU, of a thermodynamic system is equal to the energy gained as heat, Q, less the thermodynamic
work, W, done by the system on its surroundings.

U=Q-W

For processes that include transfer of matter, a further statement is needed: With due account of the
respective fiducial reference states of the systems, when two systems, which may be of different chemical
compositions, initially separated only by an impermeable wall, and otherwise isolated, are combined into
a new system by the thermodynamic operation of removal of the wall, then

U0 = U1 + U2

where U0 denotes the internal energy of the combined system, and U1 and U2 denote the internal energies
of the respective separated systems.

Adapted for thermodynamics, this law is an expression of the principle of conservation of energy, which
states that energy can be transformed (changed from one form to another), but cannot be created or
destroyed.

Internal energy is a principal property of the thermodynamic state, while heat and work are modes of
energy transfer by which a process may change this state. A change of internal energy of a system may be
achieved by any combination of heat added or removed and work performed on or by the system. As a
function of state, the internal energy does not depend on the manner, or on the path through intermediate
steps, by which the system arrived at its state.

Second Law

The second law of thermodynamics states: Heat cannot spontaneously flow from a colder location to a
hotter location.

This law is an expression of the universal principle of decay observable in nature. The second law is an
observation of the fact that over time, differences in temperature, pressure, and chemical potential tend to
even out in a physical system that is isolated from the outside world. Entropy is a measure of how much
this process has progressed. The entropy of an isolated system which is not in equilibrium will tend to
increase over time, approaching a maximum value at equilibrium. However, principles guiding systems
that are far from equilibrium are still debatable. One of such principles is the maximum entropy
production principle. It states that non-equilibrium systems behave such a way as to maximize its entropy
production.

In classical thermodynamics, the second law is a basic postulate applicable to any system involving heat
energy transfer; in statistical thermodynamics, the second law is a consequence of the assumed
randomness of molecular chaos. There are many versions of the second law, but they all have the same
effect, which is to explain the phenomenon of irreversibility in nature.

Third Law

The third law of thermodynamics states: As the temperature of a system approaches absolute zero, all
processes cease and the entropy of the system approaches a minimum value.

This law of thermodynamics is a statistical law of nature regarding entropy and the impossibility of
reaching absolute zero of temperature. This law provides an absolute reference point for the determination
of entropy. The entropy determined relative to this point is the absolute entropy. Alternate definitions
include "the entropy of all systems and of all states of a system is smallest at absolute zero," or
equivalently "it is impossible to reach the absolute zero of temperature by any finite number of
processes".

Absolute zero, at which all activity would stop if it were possible to achieve, is −273.15 °C (degrees
Celsius), or −459.67 °F (degrees Fahrenheit), or 0 K (kelvin), or 0° R (degrees Rankine).

HOW THERMODYNAMICS IS APPLIED AT A BREWING COMPANY

Heating the Wort

Much of brewing depends upon managing heat: The grain and water are heated to mashing temperature,
and then the mash must be held at that temperature for the enzymes to do their job. Too low of a
temperature makes the enzymes sluggish while too high of a temperature destroys them. Even within the
acceptable range, higher temperatures will eventually result in more alcohol and more body with the same
grain and yeast.

After mashing, the wort is boiled to prepare it for the yeast. Then the hot wort must be cooled to a yeast-
friendly temperature, and then it must be kept at this temperature throughout primary fermentation. We
can use thermodynamics to not only precisely describe what is happening but predict how long each
process will take.

A mashing bucket contains a 2 kW heating element in the bottom of it. How long will it take to raise the
temperature of four gallons of 15°C (59°F) water to 65°C (150°F) for mashing? We can ask this question
and answer it using physics, but first we need to define some words:

Power of the heating element, p = 2 kW = 2000 W

Water mass, m

Specific heat (energy required to raise the temperature of 1 g by 1°C) of water, c = 4.186 J/g K

Water temperature, T

Ambient (room) temperature, Ta

Cooling coefficient (how quickly heat escapes through the bucket's sides), α = 0.20 hr-1

Change in time, dt

Change in water temperature during a change in time, dT

We can now translate some common sense statements into the language of physics. Such as, "The
element heats the water by a small amount during a short time interval, but some heat is lost through the
sides of the bucket" (Denny):

P dt = mc[dT + α(T - Ta)dt]

We can also say, "The change in water temperature over time is equal to the power divided by the energy
required to heat up that much water minus the heat lost through the sides depending on the temperature
difference":

dT/dt = P / mc - α(T - Ta)

These two statements merely describe what we can observe. However, the real power and test of a
physics model is its ability to predict what will happen. We can use our two statements to ask the
question, "What will the temperature of the mash be after t seconds?"

T(t) = Ta + P/αmc (1 - e)-αt

We can also predict how long it will take for the water to reach mashing temperature, Tm = 65°C
(150°F):

Time to mashing temperature, tm = 1/α ln(P / P-αmc(Tm - Tα) = 27 minutes

As well as predict the time it will then take to heat the mash to boiling:

Time to boiling temperature, tb = 1/α ln(P / P-αmc(Tb - Tα) = 29 minutes

We can even predict how much wort we will lose to evaporation during the boil:

Latent heat of vaporization for water, cv = 540 cal g/mol

Evaporation percentage, ε = [P - αmc(Tb - Ta)]/mcv = 11% or 1/2 gallon per hour (for a six gallon
wort)
This now allows us to make a statement regarding the power used during the entire heating process. "The
heat supplied by our heating element goes into evaporating the water plus raising the water temperature,
as well as heat lost through the bucket wall" (Denny).

P dt = εmcvdt + mc[dT + α(T - Ta)dt]

We boil the wort because it is vulnerable to bacterial contamination below 71°C (160°F) so boiling it kills
off any microbes that we do not want turning our wort into spit or snot. Such high temperatures are also
quite hostile to the microbes that we do want turning our wort into tasty beer, so we need to cool the wort
to 20-37°C (68-99°F) before adding the yeast. Quickly cooling the wort to "pitching temperature" reduces
the amount of time bacteria has to potentially take over and can cause suspended proteins will sediment
out with a "cold break," but in practice simply covering the wort and utilizing ambient cooling works fine.

We can describe the cooling process thus:

Change in temperatue over time, dT/dt = -α(T - Ta)

And then we can predict how long it will take to reach pitching temperature, Tp:

Cooling time, tp = 1/α ln[(Tb - Ta)/(Tp - Ta)]

Yeast Respiration

Energy is at the heart of brewing, like it is for most things. Malted barley contains maltose, a sugar
consisting of two glucose molecules, and yeast must break the maltose down into glucose before it can
start fermentation. It's job during the "lag time" between introduction and fermentation is producing the
enzymes that do just that. This requires oxygen, which is why insufficient yeast or oxygen fails to
produce good beer: Too much of the maltose remains.

Aerobic yeast respiration looks like this:

C6H12O6 (glucose) + 6O2 → 6CO2 + 6H2O + 688 kcal/mol

Glucose plus oxygen results (after many intervening steps) in carbon dioxide, water, and a lot of energy.
Fortunately, most of this energy is used by the yeast for reproduction. If it was waste heat, the
temperature of our 6 gallon homebrew would increase by 77°C (139°F), and we'd have steam and dead
yeast instead of beer.

Once the yeast consumes all of the oxygen in the wort, they switch to anaerobic respiration. This is what
turns the remaining sugar into ethanol alcohol, and it looks like this:

C6H12O6 (glucose) → 2C2H5OH (ethanol) + 2CO2 + 28 kcal/mol

Anaerobic respiration produces much less (only 4%) as much energy as aerobic respiration, which is why
yeast reproduces in aerobic respiration but merely survives in anaerobic respiration, so if all of the energy
produced by 1 lbs of sugar was waste heat our 6 gallon homebrew's temperature would only increase by
3°C (5°F).
While not all of the energy released by respiration heats the wort, it does result in heating. We can also
describe this process using mathematics, but we need to define some more terms first:

Yeast population p

Wort volume, V

Density of yeast cells in the wort, ρ = p/V = constant (for this example)

Surface area (top and sides through which heat is lost) of the fermentation vessel, S

Small change in temperature, dT

Small change in time interval, dt

Yeasts' ability to generate heat throughout the wort, γ

Insulating properties of the fermentation vessel, δ = amount of heat lost through the walls

Cooling coefficient, α = Sδ/mc

Now we can make the statement, "The heat released by yeast catabolizing sugar during a short time
interval increases the wort temperature throughout the volume, but some of this generated heat is lost
through the surface," (Denny):

Change in temperature, dQ = mc dT = γρV dt = δS(T - Ta)dt

We can also predict the temperature that the wort will reach during the fermentation phase:

Yeast temperature, Ty = Ta + γρV/Sδ

These statements assume that the yeast population remains constant, which isn't a good assumption.
We've seen that yeast population rises exponentially then crashes once it runs out of nutrients. A better
statement accounts for changing yeast population. Homebrewers also need to heat their wort during
fermentation to keep the temperature within the yeast's comfort range, so we need to add something for
this external power supply.

Time-dependent population, p(t)

External power supply applied to the bucket after pitching the yeast, Phb = 30 W for 12 hours

This allows us to make the more complete statement that, "The wort temperature increases due to yeast
activity and due to external heating; all the while heat is being lost to the cooler environment," (Denny):

Change in temperature over time, dT/dt = γ/mc p(t) + Phb/mc - α(T - Ta)

This statement tells us something important about different brewing setups: Homebrewers lose too much
heat during brewing, so they have to heat their wort. This is due to the high ratio of vessel surface area, S,
to wort volume. Larger microbrewers and macrobrewers have the opposite proble. Their yeast produces
too much heat so, before refrigeration, they purposefully used vessels with as large