Hydrogeochemistry
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Transcript Hydrogeochemistry
Thermodynamics
Thermodynamics
Kinetics
Way to calculate if a reaction will occur
Way to determine the rate of reactions
Thermodynamic equilibrium rarely
attained:
Biological processes – work against thermo
Kinetic inhibitions
Thermodynamics very useful
Good approximation of reactions
Tells direction a reaction should go
Basis for estimated rates
Farther from equilibrium, faster rate
Thermodynamic definitions
System – part of universe selected for
study
Surroundings (Environment) – everything
outside the system
Universe – system plus surroundings
Boundary – separates system and
surroundings
Real or imagined
Boundary conditions – solutions to Diff Eq.
Types of systems
Open system
Closed system
Exchanges with surroundings
Mass, also heat and work
no exchange of matter between surrounding
and system, energy can be exchanged
Isolated system
there is no interaction with surroundings, no
exchange of energy or matter
Steady state system
Flux in = flux out
There can be exchange, but no change in
total abundance
Parts of Systems
Phase – physically and chemically
homogeneous region
Example: saturated solution of NaCl
Species – chemical entity (ion, molecule,
solid phase, etc.)
E.g. NaCl (solid) + H20 (liquid)
Also Na+, Cl-, OH-, H+, NaClo, others
Components
Minimum number of chemical entities required
to define compositions of all species
Many different possibilities
Na+, Cl-, H+, OH NaCl – H2O
Thermodynamic Properties
Extensive
Depends on amount of material
E.g., moles, mass, energy, heat, entropy
Additive
Intensive
Don’t depend on amount of material
Concentrations, density, T, heat capacity
Can’t be added
State function
a property of a system which has a specific
value for each state (e.g., condition)
E.g., 1 g water @ 25º C
A couple of state functions for this sytem are
amount of mass (1 g) and T (25º C)
There are others we will learn about
Path independent
E.g., state would be the same if you condensed
steam or melted ice
For the values of the state functions, it doesn’t
matter how the state got there
Thermodynamic Laws
Three laws – each derives a “new” state
function
0th law: yields temperature (T)
1st law: yields enthalpy (H)
2nd law: yields entropy (S)
Zeroth law
If two systems are in thermal equilibrium
No heat is exchanged between the systems
They have the same “temperature”
T is the newly defined state function
How is temperature defined?
Measurement of T
Centigrade
100 divisions between melting and boiling
point of water
Kelvin - Based on Charles law
At constant P and m, there is a linear
relationship between volume of gas and T
V = a1 + a2T
Where V = volume
T = temperature
a1 & a2 = constants
Size of unit is same as centigrade
V (L)
Fig. Levine
T (ºC)
• 1 mole of N2 at constant P
• Experimental results:
- extrapolation of results show intercept T
@ V = 0 is about -273ºC
- Kelvin scale based on triple point of water
- defined as being 273.16 K
First law
Change in the internal energy of a system
is the sum of the heat added (q) and
amount of work done (w) on system
Energy conserved
Three types of energy
Kinetic and potential – physically defined
Internal – chemically defined
Three forms of energy
Potential + Kinetic energy
+ internal energy
Minimum or rest energy
Here only internal energy, U
Internal energy (U)
Molecular rotation, translation, vibration and
electrical energy
Potential energy of interactions of molecules
Relativistic rest-mass energy
In thermo, a system at rest
Kinetic and potential energy = 0
Thermodynamics considers only changes in
internal energy
New state function – Enthalpy (H)
H = U + PV
PV = pressure * volume = work done
on/by the system
Units – energy, e.g. J, kJ, cal etc.
Extensive – i.e., additive.
Second Law
A system cannot undergo a cyclic process
that extracts heat from a heat reservoir
and also performs an equivalent amount
of work on the surroundings
i.e., it is impossible to build a machine that
converts heat to work with 100% efficiency
New state function
Entropy = S
Extensive = units of energy/T, e.g. kJ/K
Entropy is a variable used to defined Gibbs
free energy (G)
G used to determine equilibrium of
reactions
Equilibrium Thermodynamics
Equilibrium occurs with a minimum of
energy in system
Systems not in equilibrium move toward
equilibrium through loss of energy
If system is at constant T and P, measure
of energy of system is given by Gibbs free
energy (G)
G = f(H,S,T)
G = H - TS
G and H units = kJ (kcal)
S units = kJ/K (kcal/K)
T is Kelvin scale (K)
Imagine some system with A, B, C, and D components:
A+B↔C+D
Equilibrium A, B, C, and D present
Consider processes in system at constant
T&P
“Process” means system changes
May be chemical reaction
DG =DH - TDS
Here D is change in state:
D = State2 – State1
For all properties: G, H, T or S
When system moves toward equilibrium:
may release heat, e.g. DH < 0
entropy may increase, e.g. DS > 0
Both may happen
Thus:
DG < 0 for spontaneous reaction
G2 < G1; DG = G2 – G1 < 0
DG = 0 for process at equilibrium
Possible to calculate DG, and thus determine
(1) if reaction will occur spontaneously, and
(2) which way reaction will go.
Non-equilibrium system:
A+B→C+D
DG ≠ 0
A+B←C+D
DG ≠ 0
Equilibrium system
A+B↔C+D
DG = 0
G is an extensive state variable
The amount of G in a system is divided
among components
Need to know how G changes for each
component
First look at what variables control G
It depends on the amount of material
What is G a function of?
Want to know how G changes if all (or any)
other variable change
Change = calculus
Math Review
(on board)
If system is in thermal and mechanical
equilibrium:
G = f(P, T, n1, n2, n3…)
Then total differential:
(on board)
Infinitesimal change in G caused by
infinitesimal change in P, T, n1, n2, n3…
These are values we need to know to
know DG
Last term defined by Gibbs as chemical
potential (m)
(on board)
m is the amount that G changes (per mole)
with addition of new component
Intensive property (G extensive)
Doesn’t depend on mass of system
For one component system m = G/n
For system at equilibrium, m of all
components are identical
Equilibrium, activities, chemical
potentials
(on board)