Thermodynamics,

Systems,
Equilibrium &
Energy
Lecture 1
 Why geochemistry?
• Questions geochemistry can address:
o How and when did the matter in the cosmos form?
o How and when did the Earth form?
o How and when did the continents form?
o How do magmas form and why their diversity (basalts to granites)?
o Metamorphism transforms rocks through heat and pressure – but specifically what
temperatures and pressures?
o Our atmosphere consists mainly of N2 and O2. Was it always so?
o When did life on Earth begin?
o Why does calcite precipitate from surface waters and dissolve in deep waters?
o How do gold deposits form?
o How do oil deposits form?
o How cold were the “Ice Ages” and what caused them?
o What did our ancestors eat?
We’ll address many of these
questions in this course
To do so, we’ll need the tools of geochemistry.
In the first part of this course, we’ll acquire the tools we need.
Those tools all have their basis in physical chemistry (and ultimately physics and math), which
is where we’ll begin.
 Plan of the Course
• The Geochemical Toolbox
o Thermodynamics
o Kinetics
o Aquatic systems
o Trace elements & magmatic systems
o Isotopes
• Radiogenic
• Stable
• The Big Picture: Cosmochemistry
o Formation of the elements
o Formation of the Earth and the Solar System

• Chemistry of the Earth

 Other Info
Text: White: Geochemistry, Wiley-Blackwell, • Grading: 40% Problem Sets
ISBN 978-0-470-65668-6 (6 to 8),20% Prelim, 40%
Final Exam
• http
://www.geo.cornell.edu/geol
ogy/classes/geo455/EAS455
.
html
• Office: 4112 Snee
• Office Hours: no formal
office hours – drop by
anytime.
 Thermodynamics
• Thermodynamics is the study of energy & its transformations.
o Chemical changes involve energy; by “following the energy”, we can predict the
‘equilibrium’ state of a system and therefore the outcome of reactions.
• For example, we can predict the minerals that will crystallize from a cooling magma
or from the composition of minerals in metamorphic rocks, infer the temperature and
pressure of metamorphism
• We can predict that as the concentration of atmospheric CO 2 increases, the pH of the
ocean rises and the calcium carbonate shells of oysters and skeletons of corals will
become more soluble.
• From the abundance of certain metals in sedimentary rocks, we can infer that
oxygen was absent from the oceans in the early Earth.
• Thermodynamics uses a macroscopic approach.
o We can use it without knowledge of atoms or molecules.
o We will occasionally consider the microscopic viewpoint using statistical mechanics
when our understanding can be enhanced by doing so.
 Thermodynamics and
Kinetics
• The equilibrium state of a system is independent of any
previous state. So, for example, if we do a partial melting
experiment with rock, it should not matter if we start with a
solid and partially melt it or with a melt and partially
crystallize it, or whether we partially dissolve calcium
carbonate or partially precipitate it.
• Kinetics is the study of rates and mechanisms of reaction.
Kinetics concerns itself with the pathway to equilibrium;
thermodynamics does not. Very often, equilibrium in the Earth
is not achieved, or achieved only very slowly, which naturally
limits the usefulness of thermodynamics.
 ‘The System’
Four Kinds of Systems • A thermodynamic system is
the part of the universe we
are considering. Everything
else is referred to as the
surroundings.
o We are free to define the ‘system’
anyway we chose. However, how we
define it may determine whether or
not we can successfully apply
thermodynamics.
Equilibrium
• The equilibrium state is the
one toward which a system
will change in the absence
of constraints.
• It is time invariant on the
macroscopic scale, but not
necessarily on the
microscopic one.
 Equilibrium &
Thermodynamics
• Conundrum: strictly speaking, we can apply thermodynamics
only to the equilibrium state. If a reaction is proceeding, then
the system is out of equilibrium and thermodynamic analysis
cannot be applied!
• Solution: we imagine reversible processes in which systems are
only infinitesimally out of equilibrium. In contrast, natural
processes can proceed only in one direction and are irreversible.
• We might also imagine local equilibrium where even if the
whole system (e.g. the ocean or magma and crystals) is out of
equilibrium, we can imagine a part of it is in equilibrium (rim of
the crystal).
 Fundamental Variables
• Pressure: P
o Force/unit area

• Volume; V
• Temperature: T
• Energy: U
o Work: W
• we are mainly concerned with P-V work: pressure integrated over volume change
• Work done by a system is negative
o Heat: Q

• Entropy: S – more on that in next lecture

 Work, Heat, and Energy
• Work is done by moving a mass, M, over some distance against
a force (eg., gravity)
X
wº- ò F dx
0

dv
F =M
o Where dt

o Note that the minus sign occurs because work done by a system is negative, work done on a
system is positive.
• Heat is thermal energy that results from collective random
motion of atoms or molecules in a system (including rotational
and vibrational motions); its related to kinetic energy, such as
translational motions of molecules in a gas or vibration of atoms
in crystals.
System International (S.I.)
Units
• Pressure: Pascals, Pa ( Newton/m2 = kg-sec2/m)
o Other: atmospheres ~ bars ≈ 0.1 MPa

• Volume: m3
o Other: cm3, liter 1m3 = 106 = 103 l
o (note: liter is the standard unit in aquatic chemistry)

• Temperature: Kelvins (K)

o Other; ˚C; 1K = 1˚C, 0˚C = 273.16 K

• Energy: Joules, J (kg-m2/sec2)

o Other: calories 1J = 4.184 cal.

• Entropy: J/K
• Mass: kilograms (kg) or number of moles, N (mol);
o A mole is the amount, in grams, of an element or compound equal to its atomic or
molecular weight (e.g., 1 mol C = 12g or 0.012 kg).
 Extensive vs. Intensive
variables
• Extensive variables are ones that depend on the mass of the system, intensive ones do not.
• Which of the following are extensive?
• Pressure
• Volume
• Temperature
• Energy
• Work
• Heat
• Moles
o We can convert extensive variables to intensive ones by dividing on extensive variable by
another.

Molar volume: V =V / N
Density: V/M
 State Variables and
Equations of State
• State variables depend only on the state of the system, not on
the path taken. Not all the variables listed above are state
variables.
• Equations of state express the relationship between state
variables, e.g.:
PV=NRT
o Tells us, for a given number of moles, how temperature, volume, and pressure of an ideal
gas relate to each other; i.e., if we heat the gas, what happens to volume and pressure?
 Ideal Gas Law
PV = NRT
• Ideal gas law grew out of Boyle’s (1627-1691) experiments with gases
and was formalized by Émile Clapeyron in 1834.
o Fine as an approximation, but doesn’t work with real gases.

• An ideal gas is one in which:

o The molecules occupy no volume
o The only interactions between molecules are elastic collisions.
o When might a gas most behave ideally?
RT a
• Van der Waals Equation P= - 2
V-b V

o The b term corrects for the finite volume of molecules while the a term corrects for their interactions.
o This is still often a poor approximation to the behavior of real gases. Two geochemically important gases,
water vapor and CO2 show particularly complex P-T-V behavior.  
• R: the Gas Constant: simply converts units. (We’ll see it is the molar
equivalent of Boltzmann’s constant, which has atomic units). In essence,
this just converts units.
 General Equation of State
• There is no one solution to the ideal gas law, but we can imagine a
couple of special cases:
• Hold temperature constant
o Isothermal compressibility (β): change in volume with change in pressure at constant
temperature per unit volume: β≡ -1/V(∂V/∂P)T
• Hold pressure constant
o Coefficient of thermal expansion (α): change in volume with change in temperature at constant
pressure per unit volume 1/V(∂V/∂T)P.
• We can also write a general equation relating V, T & P:
dV = ∂V/∂T)PdT + (∂V/∂P)TdP
dV = VαdT - VβdP
o These equations are general and apply to all substances. The difference is that α and β have
simple solutions for ideal gases (NR/P and 1/T, respectively), while they are more complex
functions for real substances.
 A Note on Partial
Differential Equations
• The ideal gas law tells us that the volume of a mole of gas will
depend on 2 variables: temperature and pressure.
• Partial differential equations are a way to deal with each of
these dependencies separately:
• dV = ∂V/∂T)PdT + (∂V/∂P)TdP
• The ∂ symbol tells us this is a partial differential
• The subscript (e.g., P) says that we are holding pressure
constant.
• So the term ∂V/∂T)P expresses the change in volume with
change in temperature at constant pressure.
 • Temperature is a measure of the
Temperature average internal kinetic energy of
a system.
• How do we measure it?
o Since the volume of an ideal gas is a simple
function of T at constant P, we can use it to
construct a thermometer.
o We can arbitrarily define a scale such that
V = V0(1+γτ)
o Where τ is our measure of temperature. If so,
we might have negative τ.
o But note V cannot be negative, so there must
be a minimum value of τ: an absolute
minimum to temperature.
o The absolute minimum of T occurs where
the volume of an ideal gas is 0.
• Always use the absolute scale
(K) in thermodynamic
calculations.
 Zeroth Law
• Two bodies in thermal equilibrium have the same temperature.
• Two bodies in equilibrium with a third body are in equilibrium
with each other.
The Three E’s
Energy, Entropy and Enthalpy
 The First Law
• Statements:
o Energy is conserved in all
transformations
o Heat and work are
equivalent (the sum of the
two is always the same).
o Change in energy of a
system is independent of the
path taken.
o This might seem obvious to
us, but it wasn’t when James
Joule proposed it in 1843.

James Joule
Brewer, Scientist
 The First Law
• Statements:
o Energy is conserved in all transformations
o Heat and work are equivalent (the sum of the two is always the same).
o Change in energy of a system is independent of the path taken.
• Mathematically: ΔU = Q +W
• The First Law implies that energy change involved when a system goes from one
state to another (e.g., convert gasoline to CO2 + H2O or liquid water to ice) is path
independent and thus that energy is a state variable. Heat and work are not.
• State variables have exact differentials (heat and work do not).
o (we are mainly concerned with energy changes, not absolute amounts).
• (Of course, the First Law had to be tweaked because energy can be created out of
mass. This turns out to be important because this energy source powers not only the
Sun, and hence many processes at the surface of the Earth, it also powers, in part, the
Earth’s interior and geologic processes such as plate tectonics. That need not concern
us until much later in the course. The revised version of the first law is mass-energy
conservation.)
 State Functions & Path
Independence
• State functions are path independent and have exact differentials.
• Think about an internal combustion engine. Chemical energy is
released by burning gasoline. Some of that energy goes into heat
and some to work. There is no fixed rule about how much goes
to each – it depends on your engine design (engineers work to
increase the amount going into work).
• Therefore, heat and work cannot be state functions.
• However, no matter how you design the engine, the sum of heat
and work for a given amount of (fully) combusted gasoline is the
same.
• Energy is path independent and a state function.
 State Functions & Path
Independence
• Consider again:
dV = (∂V/∂T)PdT + (∂V/∂P)TdP
• Because V (or U) is a state
function, in a transformation of P
and T, the order and way in which
we raise temperature and pressure
does not matter: the final volume
or energy will be the same.
• Hence we can integrate the two
parts of above equation separately.
o Caveat: the compressibility and thermal
expansion terms are themselves be functions of
T and P,
 State Functions & Exact
Differentials
• State functions have exact differentials.
o (These are not something new to you, they are the kind you have learned about in
calculus).
o This means we can obtain (in principle anyway) an exact solution if we differentiate or
integrate them.
• Exact differentials have the property that the cross differentials
are equal (in other words, if we differentiate by two separate
variables, the order doesn’t matter).
o Again, this is what you learn in calculus.

• Consider dV = (∂V/∂T)PdT + (∂V/∂P)TdP

• If V is a state function, then (∂V2/∂T∂P)= (∂V2/∂P∂T)
• This is not true of non-state functions like work and heat.
 Work
• Is Work done by an ideal gas a state function?
o Work is:

dW = -PdV
o Expanding the dV term, we have
éæ ö æ ö ù
ê ¶V ¶V
dW =- P êç ÷ dT +ç ÷ dP úú
êç
è ¶T ÷
øP ç
è¶P ÷
øT ú
ë û

• Substituting for (∂V/∂T)P and (∂V/∂P)T

dW =- NRdT + NRT dP
P
¶NR ¹ ¶(NRT / P)
¶P ¶T