GEOCHEMISTRY IN

GEOTHERMAL
By
ZAINAL ABIDIN
EMAIL ; zainl53@yahoo.com , AbidinZ@starenergy.co.id
PROGRAM GEOCHEMISTRY IN GEOTHERMAL

BASIC CHEMISTRY

SOLUTE GEOCHEMISTRY

NATURAL ISOTOPES AND TRACER

TECHNIQUES

GAS GEOCHEMISTRY AND MONITORING

 Physical Chemistry , P. W Atkins
Stable Isotope Geochemistry, Jochen Hoefs
Stable Isotope Hydrology, IAEA
Radiotracer Application in Industry, IAEA
Geochemical Technique for the Exploration and Exploitation of Geothermal
Energy , Prof Dr L . Marini
Collection and Analysis of Geotherml and Volcanic Waters and Gas Discharge,
W.F Giggenbach and R.L Goguel
Gas Geochemistry as Link between Geothermal Exploration and Exploitation,
F.DAmore
Isotope and Chemical Techniques in Geothermal Exploration , Development
and Use ,Edited by Stefan Arnorsson
Chemistry and geothermal System, A.J Ellis and W.A.J Mahon
Geothermal Energy, An Alternative Resource for the 21st Century, H Gupta and
S Roy ,Elsevier , Oxford UK, 2007
Geothermal Plant, Principles, Applications, Case Studies and Environment
Impact, Ronald DiPippo, Dartmouth , Massachusetts, May 2007
 DEFINISI
Geochemistry, study of the chemical changes on the
earth
More specifically, it is the study of the absolute and
relative abundances of chemical elements in the
minerals, soils, ores, rocks, water, and
atmosphere of the earth and the distribution and
movement of these elements from one place to
another as a result of their chemical and physical
properties
Geochemical studies also include the study of
isotopes of chemical elements, especially their
abundance and stability in the universe
 Basic Chemistry
Periodic table
Atomic and Chemical bond
Acid Base
Chemical Equilibrium
Ionic Strength
Chemical Thermodinamics
ATOM
 Properties derived from outer e -

Ionization potential energy required to

remove the least tightly bound electron
Electron affinity energy given up as an
electron is added to an element
Electronegativity quantifies the tendency
of an element to attract a shared electron
when bonded to another element.
 Ionic and Covalent Bond
Elements on the right and top of the periodic
table draw electrons strongly
Bonds between atoms from opposite ends
more ionic, diatomics are 100% covalent
Bond strength Covalent>Ionic>metallic
Affects hardness, melting T, solubility
Bond type affects geometry of how ions are
arranged
More ionic vs. covalent = higher symmetry
 Types of Chemical Bonds
Ionic bonding

Polar covalent bonding

Covalent bonding
 Ionic bonding

Ionic substances are formed when an atom that

loses electrons relatively easily react with an
atom that has a high affinity for electrons.
ex. metal-nonmetal compound
23
Na11 35,5
Cl17 40
Ar18
e e

1e
7e
8e 8e
8e 8e
2e 2e
2e

Na+ Cl-
Inert/non reactive

NaCl
Ionic bond
 Covalent Bonding
Electron are shared by nuclei
 Covalent bond Intan and Graphite
1
H1 12
C6

1e C C
4e

H 2e
C C
e
stable C
e

H e e C e e
H CH4
e

H
 Polar Covalent Bonding
A polar bond is a covalent bond in which there
is a separation of charge between one end and
the other , in other words in which one end is
slightly positive and the other slightly negative.
 2e 5e
7 N

NH3 + H2O ----------------- NH4OH

NH4OH =========== NH4+ + OH-

 Polaritas Senyawa H2O
Ethanol larut dalam air
Ethanol

H+
Larutan HCl

Cl-
Sebutkan Ikatan Kimia dan Structure Molekul
dari senyawa dibawah ini :

1. KI
2. N2
3. NaSO4
4. Benzena (C6H6)
5. MgBr2
6. SiO2
7. H2CO3
8. CaCl2
9. Fe
10.CCl3F
 ASAM BASA AND KESETIMBANGAN KIMIA
Definisi :

a.Archenius :
- Asam adalah senyawa yang dapat melepaskan ion H + apabila dilarutkan dalam air
- Basa adalah senyawa yang dapat melepaskan ion OH - apabila dilarutkan dalam air

b. Bronstead-Lowry :
- Asam adalah senyawa yang dapat menjadi donatur proton
- Basa adalah senyawa yang dapat menerima proton

c. Lewis
- Asam adalah senyawa yang dapat menerima sepasang electron
- Basa adalah senyawa yang dapat memberi sepasang electron

Contoh ;
H+
HCL ---------- H +
+ CL -

NaOH ---------- Na+ + OH-
: O :H-

 Conjugate Acid-Base Pair
Conjugate acid-base pair consists of
two substances related to each other by
the donating and accepting of a single
proton.
 An Acid is Dissolved in Water
+ -
HA(aq)+H2O(l) H3O (aq)+A (aq)

acid base conjugate conjugate

acid base

[ H 3O ][ A ] [ H ][ A ]
Ka
[ HA] [ HA]
K a : acid dissociation constant
 Water as an Acid and a Base
+ -
2H2O(l) H3O (aq)+OH (aq)

Water is the common amphoteric substance.

Kw=[H3O+][OH-]=110-14 ion-product constant
pH=-log[H+]
 KEKUATAN ASAM - BASA
H2O bersifat netral pH = 7

H2O ========= H+ + OH-

[H+] [OH-]
Kw =----------------- = 10-14
[H2O]

[H+] [OH-] = 10-14

P(-log) H = 7 -------> pH + pOH = 14

pH < 7 ------- Acid

pH > 7 -------- base

 Strong Acids/ Bases
Strong Acids more readily release H+ into
water, they more fully dissociate
H2SO4 2 H+ + SO42-
Strong Bases more readily release OH- into
water, they more fully dissociate
NaOH Na+ + OH-

Strength DOES NOT EQUAL Concentration!

 ASAM KUAT DAN ASAM LEMAH

ASAM KUAT :

HCl ----------------- H+ + Cl- Ka = 1

1N 1N 1N

ASAM LEMAH :

HAc ========== H+ + Ac- Ka = 10-4,75

1N >1N >1N
x Ka=[H][Ac]/[Hac]
x
 BASA KUAT DAN BASA LEMAH

Basa Kuat :

NaOH -------------- Na+ + OH- Kb = 1

1N 1N 1N

Basa Lemah :

NH4OH ========== NH4+ + OH- Kb = 10-4,7

1N >1N >1N
 ASAM- BASA POLYPROTIC
Asam Kuat Polyprotic :

H2SO4 -------------- 2 H+ + SO42- Ka = 1

1N 2N 1N

Asam Lemah Polyprotic :

H2CO3 =========== H+ + HCO3- K1 = 10-6,35

1N >1N >1N

HCO3- =========== H+ + CO32- K2 = 10-3

>> 1N >> 1 N
Practice :

Hitung PH dari

1. 0,00025 N HCl
2. 0,0045 N H2SO4
3. 0,065 N HAc
4. 0,05 N NH4OH
5. 0,00075 N NaOH
 pH Buffer
Buffer adalah apabila suatu asam lemah ditambahkan
dengan garamnya
HAc =========== H+ + Ac- Ka = 10-4,75
0,2 N

NaAC -------------- Na+ + Ac-

0,5 N

[Ac-]
pH = PKa + log --------
[HAc]

[Ac-] = Salt concentration (Cg)

[Hac] = Acid concentration (Ca)
 CHEMISTRY EQUILIBRIUM
Material Equilibrium

(a) Chemical equilibrium, which is

equilibrium with respect to conversion of
one set of chemical species to another set.
Example : Acid-basic weak, water-mineral
, gas-water, gas-gas
(b) Phase equilibrium, which is equilibrium
with respect to transport of matter between
phases of system.
Example : water liquid-gas-solid etc
H2O+CO H2+CO2
H2O+CO H2+CO2
2NO2(g) N2O4(g)
 Manipulating the Equilibrium
There is a principle that can be studied to
govern changes in equilibrium
Le Chateliers Principle.
Le Chateliers Principle states:
If a stress is applied to a system in dynamic
equilibrium, the system changes to relieve the
stress.
Stresses are changes in temperature, pressure,
concentration of reactants, or concentration of
products
 Concentration &
Equilibrium
Adjusting the concentrations of either reactants
or products can have dramatic impact on the
equilibrium
If we add more of reactant A to a system
at equilibrium the system will strive to
reestablish equilibrium at a new
equilibrium position.
The reaction will push to use up the
extra A and generate more C

A + 2B C DH= - 250 kJ
[A], rxn will shift toward products
 Concentration &
Equilibrium
o Adjusting the concentrations of either
reactants or products can have dramatic
impact on the equilibrium
If we add more of product C to a system
at equilibrium the system will strive to
reestablish equilibrium at a new
equilibrium position.
The reaction will push to use up the
extra C and generate more A and B
A + 2B C DH= - 250 kJ
[C], rxn will shift toward reactants
 Temp effects on
Equilibrium
o The impact of temperature
changes on an equilibrium is
dependent on if the process is
endothermic
Endothermicor exothermic
processes use energy
as a reactant, while exothermic
processes produce energy
Keq is temperature dependent
250 kJ is a product

A + 2B C DH= - 250 kJ
If T, the equilibrium shifts left
 Temp effects on Equilibrium
o The impact of temperature
changes on an equilibrium is
dependent on if the process is
endothermic or exothermic
Endothermic processes use
energy as a reactant, while
exothermic processes produce
energy
energy is a reactant

C A + 2B DH= + 250 kJ
If T, the equilibrium shifts right
Keq is TEMP dependent

Endothermic or Exothermic?
 Pressure &
Equilibrium
If A, B, and C are all gases, then the equil they
establish is pressure dependent
When the pressure is increased, the system
relieves the pressure by favoring the direction
that produces fewer gas molecules.
Pressure is # of particles dependent, the more
particles the higher the pressure
Fewer gas molecules will exert less pressure.
So, more product is formed, which overall
reduces the pressure, this is a shift right
 Pressure & Equilibrium
Conversely, a decrease in pressure will favor the
rxn that produces the most molecules
So we have a shift to the left

P, this equilibrium shifts right

A + 2B C DH= - 250 kJ

If P, this equilibrium shifts left

 Unit Chemistry
Solution Concentration Units
Quantity Symbol Units Description
moles of solute per liter
Molarity M mol/L
of solution
moles of solute per
Molality m mol/kg kilogram of solvent
moles of solute per
Mole Fraction (none) moles of solution
milligrams of solute per
Parts per million ppm mgr/kg
kilogram of solution
Parts per billion micrograms of solute
Ppb ugr/kg per kilogram of solution

mol = Berat /berat molekul = gr/BM Molar = gr/(gr/mol xV) = mol/L

mmol= mgr/BM
BM =gr/mol Molal = gr/(gr/mol xKg)= mol/kg

% =wi/(wi+wo) x 100

Wi = berat zat
Wo=berat pelarut
 Solution Concentration

Concentration = quantity of solute

quantity of solution (not solvent)
There are 3 basic ways to express concentration:
1) percentages
2) very low concentrations
3) molar concentrations

1) % concentration can be in V/V, W/W, or W/V

Like most %s, V/V and W/W need to have the same units on top and bottom.
W/V is sort of in the same units; V is mostly water and waters density is 1 g/mL or 1
kg/L

2) Expressing concentrations in parts per million (ppm) requires the unit on top to be 1,000,000
times smaller than the unit on the bottom
E.g. 1 mg/kg or g/g

3) Molar concentration is the most commonly used in chemistry. Ensure that units are
mol/L
 Data Quality Control
(charge balance)
Most common Ions ;
Cations ; Na+, K+,Ca2+,Mg2+ andLi+
Anions ; Cl- , SO42- and HCO3-
Charge balance :
meq Cations = meq Anions

meq Na + meq K + meq Ca + meq Mg +meq Li = meq Cl +meq SO4 + meq HCO3

/meq cations - meq anions/

% charge balance = ------------------------------------------ x 100
[meq cations + meq anions]
 Calculations

molar mass Avogadros number

Grams Moles particles

A Mole of Particles
Contains 6.02 x 1023 particles

1 mole C = 6.02 x 1023 C atoms

1 mole H2O= 6.02 x 1023 H2O molecules
1 mole NaCl = 6.02 x 1023 NaCl molecules
(technically, ionics are compounds not molecules so they
are called formula units)

6.02 x 1023 Na+ ions and

6.02 x 1023 Cl ions
 Gases in the Air
The % of gases in air Partial pressure (STP)
78.08% N2 593.4 mm Hg

20.95% O2 159.2 mm Hg

0.94% Ar 7.1 mm Hg
0.03% CO2 0.2 mm Hg

PAIR = PN + PO + PAr + PCO = 760 mm Hg

2 2 2

Total Pressure 760 mm Hg

Gas Analysis correction :

%N2 corr = %N2 - %O2(%N2/%O2) X = Pi/Ptot ------ Pi = X Ptot

%Ar corr = %Ar - %O2(%Ar/%O2)
 Chemistry
in the
Atmosphere

(Chemical principle
By Steven S Zumdhal ) 51
 Concentration in Gaseous
UNIT Formula Definition
Xi Xi = ni / n total Mole fraction : no of moles component i
Mole/mole in a given volume of a mixture of gases.
Xi = ni/nH2O For very low conct of gasses in steam, the
mol fraction can be given in millimol gas
per mol steam
% mol % = ni / n total x 100 Mole % ; moles of gas i in 100 mole total
gas
mmol/100 mols I = mmol gas i /100 mol steam This is common unit for the expression of
steam gas concentration in the steam phase. All
Conversion: I = 1.8 x mmol/kg other unit like mmol/kg steam and mg/kg
mmol/kg steam can be derived knowing the FW of steam
I CO2= (1.8 x I) / 44 ( 18 g/mol) or the individual formula
mg/kg weights of the gasses (CO2 =44)
wt % % = wi/100 g steam Weight persen : weight of gas i in 100
parts steam
mmol/mol total gas mmoles of gas i/moles of gas For dry gas basin
% NCG (wt/wt) gr gas / gr H2O + gr gas %NCG = non condensible gases
 IDEAL GAS LAW
PV=nRT
P = Pressure
V = Volume
T = Temperature
N = number of moles

R is a constant, called the Ideal Gas Constant

Instead of learning a different value for R for all the possible unit
combinations, we can just memorize one value and convert the units to
match R.
L atm
R = 0.0821 ----------- , R = ideal gas constant = 8.314 J / mol K
Mol K 22.4 L of ANY gas AT STP = 1 mole
2 H2O2 (l) ---> 2 H2O (g) + O2 (g)
0.32 atm 0.16 atm

What is the total pressure in the flask?

Ptotal in gas mixture = PA + PB + ...
Therefore,
Ptotal = PH2O + PO2 = 0.48 atm
Daltons Law: total P is sum of PARTIAL
pressures
Physical properties
 Van der Waals equation

a V
( P 2 )(V b) RT (V )
V n
a: the effect of intermolecular attractive forces on the gas pressure
b: nonzero volume of molecules and volume
exclusive by intermolecular repulsive force

56
57
Calculate pressure for 1 mole of CO2 at
0oC in containers with 0.05 L
Use idea gas equation

Use van der Waals equation

P = 1620 atm
58
Liquid Vapor Phase

- Saturated Liquid From State (1) to

State (2) the water maintains its liquid
phase and the specific volume increases
very slightly until the temperature
reaches close to 100C (State (2).

- Saturated Vapor if progressively

changes phase from liquid to water
vapor (steam) while maintaining the
temperature at 100C (Saturation
Temperature - Tsat) until there is no
liquid remaining in the cylinder (State4)

-Superheated If heating continues then

the water vapor temperature increases
(T > Tsat) (State (5))
Quality Region is saturated liquid-vapor mixture
Quality of the mixture as dryness factor is define
As the mass vapor dived by total of mass fluid

x = mg/m
Solved Problem 2.1 - Two kilograms of water at 25C are placed in a piston cylinder device
under 100 kPa pressure as shown in the diagram (State (1)). Heat is added to the water at constant
pressure until the piston reaches the stops at a total volume of 0.4 m3 (State (2)). More heat is then
added at constant volume until the temperature of the water reaches 300C (State (3)).
Determine (a) the quality of the fluid and the mass of the vapor at state (2),
and (b) the pressure of the fluid at state (3).

Thus v2 = V / m = 0.4 [m3] / 2 [kg] = 0.2 [m3 / kg]

 Gibbs Phase Rule

Gibbs' Phase Rule provides the theoretical

foundation, based in thermodynamics, for
characterizing the chemical state of a
(geologic) system, and predicting the
equilibrium relations of the phases (minerals,
melts, liquids, vapors) present as a function of
physical conditions such as pressure and
temperature
Definitions
Gibbs Phase Rule is expressed by the simple
formulation:
P + F = C + 2, where
P is the number of phases in the system
C is the minimum number of chemical components
required to constitute all the phases in the system
F is the number of degrees of freedom in the
system (also referred to as the variance of the
system).
Some Simple One-Component
Examples
P+F=C+2
Triple point ; conist of 3 phase and one of
Component (H2O) and have F = 0

F = ? In saturation line