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Lecture 1 - Introduction 1
GEOL 237GEOL 237Principles of Chemical GeologyPrinciples of Chemical Geology
Dr. Dr. SchradhSchradh SaentonSaenton ((จรฏฐ แสนทน))
Department of Geological Sciences
Chiang Mai University, Chiang Mai, Thailand
Lecture 1 - Introduction 2
Course Objectives
To provide basic principles of geochemistry in the areas of crystal chemistry, chemical equilibria, equilibrium thermodynamics, phase rule and phase diagrams, distribution and behaviors of elements in different geologic environments.
To provide basic background for the courses of Igneous and Metamorphic Petrology (205344) and Applied Geochemistry (205481).
Lecture 1 - Introduction 3
Contact Information
Dr. Schradh SaentonOffice: GB107‐3
Phone: 0‐5394‐3417 ext. 1073
Email: [email protected]
Course Webpage
http://it.geol.science.cmu.ac.th/~ssaenton/205237/index.php
Lecture 1 - Introduction 4
Course Assessment
50% which is divided to
10% ¤aæ¹¹e¡çº40% Êoº¡ÅÒ§ÀÒ¤
Homework will be collected but not graded.
50%
For more detail, ask Dr. Burapa.
1st Half 2nd Half
¹a¡È ¡ÉÒµ �o§e¢ �ÒeÃÕ¹äÁ�¹�oÂ¡Ç �Ò 80%
¨§¨aä �à aºo¹uÒµãË�e¢ �ÒË�o§Êoº
Lecture 1 - Introduction 5
Textbooks
Krauskopf, K.B., and D.K. Bird. 1995. Introduction to Geochemistry, 3rd Edition. McGraw‐Hill, Inc. Singapore. 647pp.
Klein, C., and Hurlbut, C.S., Jr., 1999, Manual of Mineralogy, John Wiley & Sons, New York, 681 p.
Copy of the textbook (Copy of the textbook (xeroxxerox) will be available in ) will be available in course webpage.course webpage.
Lecture 1 - Introduction 6
TOPICS (June 1 – July 27)
Crystal Chemistry
Mineral Chemistry
Thermodynamics
Aqueous Chemistry (pH, Acid‐Base, Redox, etc.)
Weathering & Soils
Diagenesis
Distribution of Elements in Secondary Environment
Lecture 1 - Introduction 7
Why study geochemistry?
Crystallography
Mineralogy
Petrology
Economic Geology
Sedimentology
etc.
Mineral Exploration
Environmental Geology
Isotope Geochemistry
Hydrogeology
etc.
BASICS APPLIED
Lecture 1 - Introduction 8
What is geochemistry?
Victor Goldschmidt defined the study of geochemistry as: “the laws governing the distribution of the chemical elements and their isotopes throughout the earth”
We are interested in understanding the different ways in which elements move whether in the core, mantle, crust, oceans, sediments, air, space, or other planets…
Lecture 1 - Introduction 9
What do you see now?
Lecture 1 - Introduction 10
What you will know after this class!!
FeS2 + 3.5 O2 + H2O Fe2+ + 2 SO42‐ + 2 H+
Fe2+ + O2 + H+ Fe3+OOH + 2 H+
O2 diffusion
Bacteria/ archea Fe oxidizers, S oxidizers
Light photochemical rxns, phototrophic organisms??
CH2O + FeOOH Fe2+ + CO2
CH2O + SO42‐ HS‐ + CO2
Lecture 2 - Crystal Chemistry 1
Crystal Chemistry
Review: Atoms
Atomic Structure
Bonding
Lecture 2 - Crystal Chemistry 2
Objectives
To understand that “physical properties” of minerals are closely related to “crystal structure.”
And, crystal structure depends on types of bonding and coordination number.
Then, types of bonding is strongly related to types of atoms whereas coordination number depends on charge+size of atoms.
Lecture 2 - Crystal Chemistry 3
Atoms
ในอะตอมทเปนกลาง จะมจานวนอเลกตรอนเทากบโปรตอนเสมอ
Lecture 2 - Crystal Chemistry 4
Classical Model of Atoms
Lecture 2 - Crystal Chemistry 5
Does electron exist?
ÁÕoo¡Òʾºo ieÅ硵Ão¹ 99% ã¹¾ é¹·ÕèæÃe§Ò
Lecture 2 - Crystal Chemistry 6
How do electron(s) live in atoms?
From quantum mechanics, electrons have their own orbitals (ǧo¤¨Ã).Each orbital has unique energy level and ways of orbiting around nucleus.
Each electron has its own set of quantum numbers.
Electron cannot be seen or pictured precisely. Only probability of finding electrons can be calculated.
Lecture 2 - Crystal Chemistry 7
Quantum Numbers
Lecture 2 - Crystal Chemistry 8
Energy Levels and Probability of Finding Electrons
Lecture 2 - Crystal Chemistry 9
Electronic Configuration¡Òèa´eÃÕ§o ieÅ硵Ão¹ ¨aµ�o§eµiÁŧã¹Ãa aºªaé¹¾Åa§§Ò¹µèíÒÊu´¡ �o¹ æÅ �Çe¾ièÁÃa aº¾Åa§§Ò¹ä»eÃèoÂæ ¨¹¤Ãº¨íҹǹ e‐
Lecture 2 - Crystal Chemistry 10
µÒÃÒ§¸Òµuä �¨a´¡Åu�Á¸Òµu·ÕèÁÕo ieÅ硵Ão¹Ç§¹o¡Êu 溺e ÕÂÇ¡a¹äÇ��Ç¡a¹
Lecture 2 - Crystal Chemistry 11
Electronic Configuration of Na
Lecture 2 - Crystal Chemistry 12
Electronic Configuration of Si
Lecture 2 - Crystal Chemistry 13
Electronic Configuration of Fe
Lecture 2 - Crystal Chemistry 14
ÙµÒÃÒ§ 4.5 ˹�Ò 181‐182 (KH‐Chap4)
« è§ä � List ¡Òà a´eÃÕ§o ieÅ硵Ão¹¢o§¸Òµuµ �Ò§æ äÇ �·aé§ËÁ´
Lecture 2 - Crystal Chemistry 15
Ionization Energy (IE)
¸Òµu·ÕèÁÕ IE µèíÒæ ¨aÁÕæ¹Ço¹ �Á·Õèµ�o§¡ÒÃeÊÕÂo ieÅ硵Ão¹ä �§�Ò ¨ §oÂÒ¡oÂÙ�e» �¹äooo¹ºÇ¡ ÁÒ¡¡Ç�Òʶҹa»¡µi
Lecture 2 - Crystal Chemistry 16
Electronegativity (EN)
¸Òµu·ÕèÁÕ EN ÊÙ§æ µ�o§¡Ò÷Õè¨aÃaºËÃo´§o ieÅ硵Ão¹ (oÂÒ¡e» �¹äooo¹·ÕèÁÕ»Ãa¨uź) e¢�ÒÁÒËÒoÂÙ�ã¹Ç§o¤¨Ãǧ¹o¡Êu´
Lecture 2 - Crystal Chemistry 17
Trend of Electronegativity
Lecture 2 - Crystal Chemistry 18
Stable Ions and Oxidation States
Lecture 2 - Crystal Chemistry 19
Energy of electrons can be used to identify types of elements and/or minerals.
Electron(s) in atom or ions will form “bond” with other atoms/ions.
Bond’s characteristics will govern properties of matter. For example, bonds will determine crystal structure for solids
Importance of Electrons
Lecture 2 - Crystal Chemistry 20
Use of electron energy to identify elements and/or minerals.
X‐Ray Mineralogy
Lecture 2 - Crystal Chemistry 21
Hydrogen Atom
Lecture 2 - Crystal Chemistry 22
Bombarding atoms with high energy electrons.
Lecture 2 - Crystal Chemistry 23
Characteristic Wavelengths
Lecture 2 - Crystal Chemistry 24
Use of Characteristic Wavelength
X‐ray diffraction for determination of types of minerals.
Example:
Target = Cu (Copper)
Filter = Ni (Nickel)
Lecture 2 - Crystal Chemistry 25
X‐ray diffractionLaue Method
Powder Method
θ λ=2 sind n
Lecture 2 - Crystal Chemistry 26
Importance of Electrons
Energy of electrons can be used to identify types of elements and/or minerals.
Electron(s) in atom or ions will form “bond” with other atoms/ions.
Bond’s characteristics will govern properties of matter. For example, bonds will determine crystal structure for solids
Lecture 2 - Crystal Chemistry 27
Types of Bonding
Ionic Bond
Covalent Bond
Metallic Bond
Van der Waals, Hydrogen Bonds
e» �¹¾a¹¸ae¤ÁÕÃaËÇ�Ò§oaµoÁ
e» �¹¾a¹¸ae¤ÁÕÃaËÇ�Ò§oaµoÁ æÅa/ËÃo oÁeÅ¡uÅ
Lecture 2 - Crystal Chemistry 28
Ionic Bond
Two ions are held together by electrostatic forces.
One element gains electron while another loses electron.
This is because the difference in EN is high.
( )20.25 E%Ionic 100 1 e− Δ⎡ ⎤= −⎣ ⎦
Lecture 2 - Crystal Chemistry 29
Example of Ionic Bond ‐ NaCl
ÁÕ¡Òö �ÒÂe·o ieÅ硵Ão¹¨Ò¡oaµoÁ¢o§o«e ÕÂÁä»ÊÙ�oaµoÁ¢o§¤ÅoÃÕ¹ e¾ èoãË�¤Ãº¡®oo¡eµµ (Octet Rule)
Lecture 2 - Crystal Chemistry 30
Covalent Bond
EN of two atoms are similar.
Sharing of outer‐shell electrons occurs to satisfy Duet or Octet rules.
Lecture 2 - Crystal Chemistry 31
Metallic Bond
Not enough electrons to satisfy Octet rule.
Therefore, sharing of electrons among atoms occur throughout the structure.
Lecture 2 - Crystal Chemistry 32
Van der Waals Bond
Very weak bond due to the polarization of atoms.
S8 Ring
Lecture 2 - Crystal Chemistry 33
Hydrogen Bond
Dipole‐Dipole interactions between molecules.
Water Molecule
Ice Crystal
Lecture 2 - Crystal Chemistry 34
Lecture 3 - Crystal Chemistry (Cont'd) 1
Crystal Chemistry
Ionic Radii, Coordination Number
Lecture 3 - Crystal Chemistry (Cont'd) 2
Examples of ionic radii (A = 10‐10 m)
Lecture 3 - Crystal Chemistry (Cont'd) 3
Atomic/Ionic Radii: How to find them?
Not easy to measure or quantify.May be determined from halving the distance between adjacent atoms (for metal).For ionic solids, radius is calculated from electrostatic force or, nowadays, from x‐ray diffraction.
Lecture 3 - Crystal Chemistry (Cont'd) 4
Electrostatic Force
( )( )2
+ −
=q q
F kd
+ −
′=q q
U kd
Lecture 3 - Crystal Chemistry (Cont'd) 5
ã¹»�¨ uºa¹ ÃaÈÁÕäooo¹¨aËÒä �¨Ò¡¡ÒÃÇa ÃaÂaË�Ò§ÃaËÇ �Ò§oaµoÁo´Â㪠�e·¤¹i¤ x-ray diffraction
« 觨a·íÒ¡ÒÃÇa´ÃaÈÁÕäooo¹¨Ò¡ÊÒûÃa¡oºËÅÒÂæ ª¹i´ ·ÕèÁÕeÅ¢o¤ooà � i¹ªaè¹ (Coordination Number) µ�Ò§æ ¡a¹ æÅ�ǹíÒÁÒËÒ¤ �Òe©ÅÕèÂ
Lecture 3 - Crystal Chemistry (Cont'd) 6
Coordination Number (C.N.)
CN = The number of closest neighbors around a specific atom or ion
CN = 2, 3, 4, 6, 8, or 12 depending on the radius ratio between cation(+) and anion(‐)
Lecture 3 - Crystal Chemistry (Cont'd) 7
Lecture 3 - Crystal Chemistry (Cont'd) 8
Lecture 3 - Crystal Chemistry (Cont'd) 9
ÁÕ»�¨ aÂoaä÷Õè·íÒãË�¸Òµuª¹i´e ÕÂÇ¡a¹ ÁÕeÅ¢o¤oo´ie¹ªaè¹äÁ�eËÁo¹¡a¹?
oaµÃÒÊ�ǹÃaÈÁÕ¢o§äooo¹ºÇ¡/ź ËÃo+
−
RR
A
X
RR
ËÃo
Lecture 3 - Crystal Chemistry (Cont'd) 10
Lecture 3 - Crystal Chemistry (Cont'd) 11
Halite Structure (NaCl)
Lecture 3 - Crystal Chemistry (Cont'd) 12
Fluorite Structure (CaF2)
Lecture 3 - Crystal Chemistry (Cont'd) 13
Theoretical limiting radius ratioCN = 8
+
− = = 0.732A
x
R RR R
A
X X
XX
Lecture 3 - Crystal Chemistry (Cont'd) 14
Theoretical limiting radius ratioCN = 6
+
− = = 0.414A
x
R RR R
A
X X
X X
Lecture 3 - Crystal Chemistry (Cont'd) 15
Theoretical limiting radius ratioCN = 3
+
− = = 0.155A
x
R RR R
Lecture 3 - Crystal Chemistry (Cont'd) 16
Change in CN due to atomic radii
CN=6
CN=8
Lecture 3 - Crystal Chemistry (Cont'd) 17
ã¹o¤Ã§Êà �Ò§¢o§¼Å¡ äooo¹ºÇ¡ ¨a¾ÂÒÂÒÁoÂÙ�Ë�Ò§¡a¹ÁÒ¡·ÕèÊu´o´Âãª�Çi¸Õ¡ÒÃÊà �Ò§ Coordination Polyhedra
« 觨aÁÕ¡Òà share ÁuÁ (corner) ËÃo ¢oº (edge) ËÃo ˹ �Ò (face)
Lecture 3 - Crystal Chemistry (Cont'd) 18
µaÇo �Ò§ Coordination Polyhedra (¡Òà share ¡a¹¢o§ polyhedra o´Âäooo¹Åº) ¢o§ Tetrahedra
มม ขอบ หนา
Lecture 3 - Crystal Chemistry (Cont'd) 19
µaÇo �Ò§ Coordination Polyhedra (¡Òà share ¡a¹¢o§ polyhedra o´Âäooo¹Åº) ¢o§ Octahedra
มม ขอบ หนา
Lecture 3 - Crystal Chemistry (Cont'd) 20
Pauling’s Rule of Ionic Structure
Lecture 3 - Crystal Chemistry (Cont'd) 21
Pauling’s Rule of Ionic Structure
Lecture 3 - Crystal Chemistry (Cont'd) 22
CN=8, CN=6
Lecture 3 - Crystal Chemistry (Cont'd) 23
CN=4, CN=3
Lecture 3 - Crystal Chemistry (Cont'd) 24
Pauling’s Rule of Ionic Structure
Lecture 3 - Crystal Chemistry (Cont'd) 25
Pauling’s Rule of Ionic Structure
Rule #4:
¶�Òã¹o¤Ã§Êà �Ò§¢o§¼Å ¡ ÁÕäooo¹ºÇ¡ËÅÒÂæ ª¹i oÂÙ��Ç¡a¹ äooo¹ºÇ¡·ÕèÁÕ¢¹Ò´eÅç¡Êu´æÅaÁÕ CN µèíÒÊu´ ¨a
äÁ�ÁÕ¡Òà share polyhedra
Lecture 3 - Crystal Chemistry (Cont'd) 26
ÊÃu» – Pauling’s Rules
µ �o§¡ÒÃãË �e¡i´¤ÇÒÁÊÁ uÅÃaËÇ�Ò§»Ãa¨uºÇ¡æÅaźã¹o¤Ã§Êà �Ò§¢o§¼Å ¡ o´Â¡ÒÃeÃÕ§µaǨaµ �o§·íÒãË �»Ãa¨uª¹i´e ÕÂÇ¡a¹oÂÙ�Ë �Ò§¡a¹ÁÒ¡·ÕèÊu´
Lecture 3 - Crystal Chemistry (Cont'd) 27
Bond Strength
Ça´¨Ò¡¨u´ËÅoÁeËÅÇ
Lecture 3 - Crystal Chemistry (Cont'd) 28
Bond Strength
Ça´¨Ò¡¤ÇÒÁæ¢ç§
Lecture 3 - Crystal Chemistry (Cont'd) 29
General Rule about Bond Type
Lecture 3 - Crystal Chemistry (Cont'd) 30
Lecture 4 - Crystal Chemistry (Cont'd) 1
Crystal Chemistry (cont’d)
Polymorphism
Isomorphism
Ionic Substitution
Lecture 4 - Crystal Chemistry (Cont'd) 2
Review
1. Radius Ratio (R+/R‐)2. Coordination Number (CN)3. Coordination Polyhedra4. Pauling’s Rules of Ionic Structure
1. Radius ratio determines coordination number.2. Electrostatic valency principle (e.v. = |z|/CN)3. Coordination polyhedra of anion will result in sharing
corners rather than edges or faces.4. For multi‐cations solid, smallest cation with lower C.N.
will not form coordination polyhedra.
Lecture 4 - Crystal Chemistry (Cont'd) 3
Example Calculation of e.v.
ze.v.
C.N.=
e.v. = electrostatic valency
Na+: CN=6
Cl‐: CN=6
1e.v.
6= +
1e.v.
6= −
Lecture 4 - Crystal Chemistry (Cont'd) 4
Exercise #1
Example calculation of e.v.
Example calculation of NaCl size from density
Lecture 4 - Crystal Chemistry (Cont'd) 5
Polymorphism
A substance that can have more than one crystal structures.Why?
Ions making up compounds can crystallize either structure.Important Factors: Temperature & Pressure
Examples?Carbon (C)Al2SiO5
Sulfur (S)Quartz (SiO2)
Lecture 4 - Crystal Chemistry (Cont'd) 6
Sulfur: Temperature
Temperature
“Rhombic” Structure
“Monoclinic” Structure
96 °C Transition Temperature
Lecture 4 - Crystal Chemistry (Cont'd) 7
Carbon: Temperature + Pressure
Lecture 4 - Crystal Chemistry (Cont'd) 8
Al2SiO5: Temperature + Pressure
Lecture 4 - Crystal Chemistry (Cont'd) 9
= Dimorphous
Lecture 4 - Crystal Chemistry (Cont'd) 10
Dimorphous Minerals
Lecture 4 - Crystal Chemistry (Cont'd) 11
Isomorphism
Two substances are “isomorphous” if they have similar crystal structures but different chemical formulae.
OlivineOlivine: (Mg,Fe)2SiO4 has two “end members.”
Mg2SiO4 Fe2SiO4Mg1.3Fe0.7SiO4(forsterite) (fayalite)
Lecture 4 - Crystal Chemistry (Cont'd) 12
Ionic Substitution
Replacement of one cation in crystal structure by another cation.
¡ÒÃæ·¹·Õèäooo¹ºÇ¡ã¹o¤Ã§Êà �Ò§´ �ÇÂäooo¹ºÇ¡oÕ¡µaÇ˹ è§ o´Â·Õèo¤Ã§Êà �Ò§äÁ �e»ÅÕè¹æ»Å§Examples:
olivine (Mg‐Fe)
plagioclase (Ca,Na)
Lecture 4 - Crystal Chemistry (Cont'd) 13
e˵uã´¨§e¡i´¡ÒÃæ·¹·Õè¡a¹ä´ �?
»Ãa¨ueËÁo¹ËÃoã¡Å �e¤Õ§¡a¹ (µ �Ò§¡a¹äÁ�e¡i¹ 1)Mg(+2) ��. Fe(+2) Ëà o Ca(+2) ��. Na(+1)
¢¹Ò´¢o§ÃaÈÁÕäooo¹ã¡Å �e¤Õ§¡a¹ (µ �Ò§¡a¹äÁ�e¡i¹ 15%)Mg (0.72 Å), Fe (0.78 Å)
¾a¹¸ae¤ÁդŠ�Ò¤ŧ¡a¹ eª�¹ e»�¹¾a¹¸a·ÕèÁÕ¤ÇÒÁe» �¹äooo¹¹i¡¾oæ ¡a¹äooo¹¢o§ Fe2+ ã¹ FeS2 Áa¡äÁ�¶Ù¡æ·¹·Õè´ �Ç Mg2+ e¾ÃÒa¾a¹¸aÁÕ¤ÇÒÁe» �¹o¤ÇÒeŹ· �ÊÙ§
Lecture 4 - Crystal Chemistry (Cont'd) 14
Substitution of di‐valent cations in carbonates
Lecture 4 - Crystal Chemistry (Cont'd) 15
Lecture 5 - Crystal Chemistry (Cont'd) 1
Crystal Chemistry (cont’d)
Ionic SubstitutionSolid SolutionExsolution
Lecture 5 - Crystal Chemistry (Cont'd) 2
Ionic Substitution
¡ÒÃæ·¹·Õè¡a¹ä �¢o§oaµoÁ ·íÒãË�e¡i´ÊÒÃÅaÅÒ¢o§æ¢ç§ËÃo (Solid Solution) o´Â·Õèo¤Ã§Êà �Ò§¼Å ¡äÁ �e»ÅÕè¹æ»Å§ (æµ �oÒ¨ÁÕ¡Òúi´eºÕéÂÇ ¼i´e¾Õé¹仨ҡe iÁeÅ硹�oÂ)¡ÒÃæ·¹·Õè ¨ae¡i´¢ é¹ä �ËÅÒÂ溺
ª¹i´ æ·¹·Õè¡a¹ä �·aé§ËÁ´ ·u¡ou³ËÀÙÁiæÅa¤ÇÒÁ´a¹
eª�¹ Olivineª¹i´ æ·¹·Õè¡a¹ä �ºÒ§Ê�ǹª¹i´ æ·¹·Õè¡a¹ä �ºÒ§Ê�ǹ e©¾ÒaºÒ§ou³ËÀÙÁi
Lecture 5 - Crystal Chemistry (Cont'd) 3
Albite/Feldspar (Binary System)
Lecture 5 - Crystal Chemistry (Cont'd) 4
Feldspar/Plagioclase (Ternary System)
Lecture 5 - Crystal Chemistry (Cont'd) 5
ou³ËÀÙÁiÊÙ§
ou³ËÀÙÁi»Ò¹¡ÅÒ§
Lecture 5 - Crystal Chemistry (Cont'd) 6
Solid Solution (ÊÒÃÅaÅÒ¢o§æ¢ç§)
�A mineral structure in which specific atomic site(s) are occupied in variable proportions by two or more different elements�
�¢o§æ¢ç§ (·Õèe»�¹æà �) ·Õè« è§oaµoÁ/äooo¹¶Ù¡æ·¹·Õèä � �ÇÂoaµoÁ/äooo¹µaÇo è¹o´Â·Õèo¤Ã§Êà �Ò§äÁ �e»ÅÕè¹æ»Å§
Lecture 5 - Crystal Chemistry (Cont'd) 7
Types of solid solution
1. Substitutional SS
2. Interstitial SS
3. Omission SS
㹡ÒÃæ·¹·Õèäooo¹«è§¨aµ�o§ÁÕ¡Òê´eªÂ»Ãa¨u »Ãa¨u·ÕèÁÒª´eªÂ¨ae¢�Òä»oÂÙ�ãʹª�o§Ç �Ò§ã¹o¤Ã§Êà �Ò§«è§ÁÕoÂÙ�æÅ �Ç
㹡ÒÃæ·¹·Õèäooo¹«è§äÁ�µ�o§ÁÕ¡Òê´eªÂ»Ãa¨u äooo¹ãËÁ �¨ae¢�Òä»æ·¹·Õèäooo¹e´iÁã¹o¤Ã§ÊÃ�Ò§e´iÁ oÒ¨e» �¹¡ÒÃæ·¹·Õè溺e´ÕèÂÇæ ËÃo溺e» �¹¤Ù�
ÁÕ¡ÒÃæ·¹·Õèäooo¹»Ãa¨u¹ �oÂÊo§µaÇ´ �Ç»Ãa¨u·ÕèÁÒ¡¡Ç �Òe¾Õ§˹ 觵aÇ ·íÒãË�e¡i´ª�o§Ç �Ò§ã¹o¤Ã§ÊÃ�Ò§
Lecture 5 - Crystal Chemistry (Cont'd) 8
Substitutional SS
ÁÕ·aé§æººæ·¹·Õèä �·aé§ËÁ´ ËÃoºÒ§Ê �ǹ «è§¢¹Ò´¢o§äooo¹¨ae» �¹µaÇ¡íÒ˹´Ç�Ò¨ae¢�Òä»æ·¹·Õèä �溺ä˹
Lecture 5 - Crystal Chemistry (Cont'd) 9
Interstitial SS (การแทนทในชองวางทมอยแลว)
¡ÒÃæ·¹·Õè 2Si4+ ´ �Ç Al3+ æÅa Be2+ ¨aÁÕ»Ãa¨u¢Ò´ä» +3 ´a§¹aé¹äooo¹¢¹Ò´ãË�eª�¹ 3K+ ÊÒÁÒöe¢�Òä»oÂÙ�ã¹o¤Ã§Êà �Ò§ o´Â¨ae¢�Òä»oÂÙ�㹪�o§Ç �Ò§·ÕèÁÕoÂÙ�æÅ �Ç
Lecture 5 - Crystal Chemistry (Cont'd) 10
Omission SS
e» �¹¡ÒÃæ·¹·Õèæ ·íÒãË�e¡i´ª�o§Ç �Ò§ (vacancy) ã¹o¤Ã§ÊÃà �Ò§ «è§Áa¡e¡i´¨Ò¡¡ÒÃæ·¹·Õè¢o§äooo¹ºÇ¡»Ãa¨ uµèíÒæ Êo§µaÇ¢é¹ä» �ÇÂäooo¹ºÇ¡»Ãa¨ uÊÙ§¡Ç�Ò¨íҹǹ˹觵aÇ eª�¹ ¡ÒÃæ·¹·Õè¢o§ 2K+ �Ç Pb2+ ã¹æÃ� microcline (KAlSi3O8)
+ + ++ = +2K K Pb
Lecture 5 - Crystal Chemistry (Cont'd) 11
Solid Solution (ÊÒÃÅaÅÒ¢o§æ¢ç§)
¶ �Òe¡i´·Õèo u³ËÀÙÁiÊÙ§ oaµoÁ¨aeÃÕ§µaÇ¡a¹äÁ�e»�¹ÃaeºÕº ÊÒÃÅaÅÒ¢o§æ¢ç§¨aeÃÕÂ¡Ç �Ò disordered SS¶ �Òe¡i´·Õèo u³ËÀÙÁiµèíÒ oaµoÁ¨aeÃÕ§µaÇ¡a¹e»�¹ÃaeºÕºÁÒ¡¢é¹ ÊÒÃÅaÅÒ¢o§æ¢ç§·Õèe¡i´ ³ o u³ËÀÙÁiµèíÒæ ¨aeÃÕÂ¡Ç �Ò ordered SS
Lecture 5 - Crystal Chemistry (Cont'd) 12
Order-Disorder
Lecture 5 - Crystal Chemistry (Cont'd) 13
Exsolution
ÊÒÃÅaÅÒ¢o§æ¢ç§·Õèe¡i´ ³ o u³ËÀÙÁiÊÙ§æ (e¡i´ä �e¾ÃÒao¤Ã§ÊÃ�Ò§e¡i´¡ÒâÂÒµaÇ) æµ �eÁèo u³ËÀÙÁiŴŧ ¨ae¡i´¡ÒÃ桵aÇoo¡e» �¹¼Å ¡Êo§ª¹i´ (ËÃoÁÒ¡¡Ç�Ò¹aé¹) oo¡¨Ò¡¡a¹
A process whereby an initially homogeneous solid solution separates into two (or possibly more) distinct crystalline minerals without addition or removal of material from the sytem
Lecture 5 - Crystal Chemistry (Cont'd) 14
Albite/Feldspar (Binary System)
solvus
Lecture 5 - Crystal Chemistry (Cont'd) 15
Exsolution: example
Lecture 5 - Crystal Chemistry (Cont'd) 16
Mineral Chemistry
Chemical Formulae of the Minerals
Lecture 5 - Crystal Chemistry (Cont'd) 17
Recalculation of chemical analysis
æà �ÁÕÊÙµÃe¤ÁÕ·Õèæ¹ �¹o¹ « è§ÊÒÁÒöe»ÅÕè¹æ»Å§ä´ �ã¹Ç§¨íÒ¡a´ o´Â·Õèo¤Ã§Êà �Ò§äÁ �e»ÅÕè¹æ»Å§»�ËÒ¡ç¤o ËÅa§¨Ò¡Çie¤ÃÒaË�æà �µaÇ˹ è§æ æÅ�ǾºÇ �ÒÁÕ¸Òµ uoÂÙ�ËÅÒÂæ ª¹i´ ¨a·ÃÒºÊÙµÃe¤ÁÕ¢o§æà �µaǹaé¹ä´ �o �Ò§äÃ?
oÒ¨Çie¤ÃÒaË�o´Âãª�e·¤¹i¤ x-ray fluorescent
spectroscopy
Lecture 5 - Crystal Chemistry (Cont'd) 18
Example: Chalcopyrite (CuFeS2)
Cu:Fe:S = 1:1:2 หรอ CuFeS2
Lecture 5 - Crystal Chemistry (Cont'd) 19
Example: Sphalerite (Zn,Fe,Mn,Cd)S
เปน Solid Solution ในโครงสราง Sphalerite
Lecture 5 - Crystal Chemistry (Cont'd) 20
Example: Gypsum (CaSO4·2H2O)
ผลการวเคราะห สวนใหญจะออกมาในรปของ oxide ดงเชน กรณของแรยปซม
Lecture 5 - Crystal Chemistry (Cont'd) 21
㹡óշÕèe» �¹ solid solution ¡ÒäíҹdzËÒÊÙµÃe¤ÁÕËÃoo§¤ �»Ãa¡oº¢o§æµ �Åa end members ¨a㪠� íҹǹoo¡«ie¨¹e» �¹ËÅa¡
µaÇo �Ò§eª �¹ Olivine, Pyroxene, æÅa Amphiboleso´Â¼Å¡ÒÃÇie¤ÃÒaË�»ÃiÁÒ³¸Òµu¨aoÂÙ�ã¹ÃÙ»¢o§ wt% oo¡ä«´ �
Lecture 5 - Crystal Chemistry (Cont'd) 22
Example: Olivine Solid Solution
แร Olivine เปนสารละลายของแขงทประกอบดวย 2 end members ไดแก fosterite & fayalite
Olivine = Fo57Fa43
Lecture 5 - Crystal Chemistry (Cont'd) 23
Pyroxene Solid Solution
Pyroxene = Wo50.3En42.4Fs7.3
Ca(Mg,Fe)(Si,Al)2O6
Lecture 6 - Physical Properties of Minerals 1
Physical Properties of Minerals
Types of ElementsChemical BondingCrystal Structure
¤u³ÊÁºaµi·Ò§¡ÒÂÀÒ¾¢o§æà �¢ é¹oÂÙ�¡aº» �¨ aµ �o仹Õé
Lecture 6 - Physical Properties of Minerals 2
Physical Properties - ¤u³ÊÁºaµi·Ò§¡ÒÂÀÒ¾
Cleavage, Parting, & FractureHardnessTenacitySpecific gravityColor
StreakLusterChatoyancy & AsterismElectrical propertyMagnetic property
Lecture 6 - Physical Properties of Minerals 3
Cleavage
Cleavage = ¡ÒÃ浡e»�¹Ë¹�ÒeÃÕº¢o§æà �µÒÁÃa¹Òº·ÕèÁÕæç ´e˹ÕèÂÇã¹o¤Ã§¼Å¡o �o¹·ÕèÊu´ (ÃaÂaÃaËÇ�Ò§Ãa¹Òº = ¡Ç�Ò§)
Lecture 6 - Physical Properties of Minerals 4
¡ÒÃ浡µÒÁæ¹Ç cleavage äÁ �¨íÒe»�¹µ�o§ÊaÁ¾a¹¸ �¡aºÃÙ»¼Å¡ËÃoÃa¹Òº¢o§ crystal growth ¡çä �
Cleavage vs. Growth plane
Growth Plane = Ãa¹Òº¢o§¼Å¡·Õè˹ �ÇÂeÅç¡æ ÁÒµ�oæ ¡a¹¨¹¡ÅÒÂe»�¹¼Å¡¢¹Ò´ãË�
Lecture 6 - Physical Properties of Minerals 5
Parting & Fracture
Parting: Ëà oæ¹Çæ¡¢o§æà � « è§Áa¡¨ae¡i´¨Ò¡¡Ò÷Õè¡ �o¹æà �e¡i´¡Òà exsolution (ÊÒÃÅaÅÒ¢o§æ¢ç§æ¡µaÇoo¡¨Ò¡¡a¹e»�¹ªaé¹æ) æÅ�Çæà �Êo§µaǹÕéæ¡oo¡¨Ò¡¡a¹
Fracturing: 㹡óշÕè¾a¹¸ae¤ÁÕÁÕ¤ÇÒÁæ¢ç§æçe· �Òæ ¡a¹·u¡·iÈ·Ò§ ¡ÒÃ浡¢o§æà � aäÁ�ÁÕ·iÈ·Ò§·Õèæ¹ �¹o¹ eª�¹ æà �¤Çoµ« �eÁèo浡¨aäÁ�ÁÕ·iÈ·Ò§ËÅa¡
Lecture 6 - Physical Properties of Minerals 6
Hardness
¤ÇÒÁæ¢ç§ËÃo¤ÇÒÁ·¹·Ò¹µ �o¡Òâٴ¢ �ǹ (o´Â·Õèæà �äÁ�ÁÕ¡ÒÃ浡oo¡¨Ò¡¡a¹)
¤ÇÒÁæ¢ç§e»�¹¤u³ÊÁºaµi·Õè¢ é¹oÂÙ�¡aº¾a¹¸ae¤ÁÕ æÅa¡Òèa´eÃÕ§äooo¹ËÃo¡Åu�Áäooo¹ã¹o¤Ã§Êà �Ò§¼Å¡
Lecture 6 - Physical Properties of Minerals 7
Tenacity
BrittleMalleableSectileDuctileFlexibleElastic
ËÁÒ¶ §¤ÇÒÁ·¹·Ò¹µ �o¡Ò÷uº ¡Òú´ ¡Òúi ÏÅÏ « 觢 é¹oÂÙ�¡aºª¹i´¢o§¾a¹¸ae¤ÁÕã¹o¤Ã§Êà �Ò§
¾a¹¸aäooo¹i¡¾a¹¸ao¤ÇÒeŹ·� ¾a¹¸aæǹe´oÇÒÅÊ �¾a¹¸aoÅËa
Lecture 6 - Physical Properties of Minerals 8
Specific Gravity
¤ÇÒÁ¶ �ǧ¨íÒe¾Òa ¤ o¤ÇÒÁ˹Òæ¹ �¹¢o§æà � ËÒà �Ç ¤ÇÒÁ˹Òæ¹ �¹¢o§¹éíÒ·Õè 4o C
¤ÇÒÁ¶ �ǧ¨íÒe¾Òa¢ é¹oÂÙ�¡aº(1) ª¹i´¢o§oaµoÁ/äooo¹(2) ¡Òèa´eÃÕ§oaµoÁ/äooo¹ã¹
o¤Ã§Êà �Ò§¼Å¡
Lecture 6 - Physical Properties of Minerals 9
ColorÊÕ¢o§æà � e¡i´¢ 鹨ҡ¡Ò÷ÕèoieÅ硵Ão¹ã¹oaµoÁæÅaã¹¾a¹¸ae¤ÁÕ ¢o§¸ÒµuoÅËa·ÃÒ¹Êiªa¹ (Ê�ǹãË�e»�¹ÊÒÃÁÅ·i¹) ÁÕ¡ÒÃe»ÅÕè¹æ»Å§ orbital ËÃoe»ÅÕè¹æ»Å§Ãa aº¾Åa§§Ò¹ (oÒ¨ÁÕ¡Òà ٴe¢ �Òä»ËÃo¤ÒÂoo¡ÁÒ) ·íÒãË �e¡i´æʧÊÕµ�Ò§æ
Crystal Field Theory
Lecture 6 - Physical Properties of Minerals 10
Electrical Properties
ConductorSemi-ConductorNon-Conductor
Piezoelectric ÊÒÁÒö¹íÒä¿¿�Òä � eÁ èoãË �¤ÇÒÁ´a¹æ¡�¡�o¹æÃ�
Pyroelectric ÊÒÁÒö¹íÒä¿¿�Òä �eÁ èoãË �¤ÇÒÁÃ�o¹e»�¹¤u³ÊÁºaµi·Õè¢ é¹oÂÙ�¡aº¾a¹¸a
e¤ÁÕ æÅaª¹i´¢o§oaµoÁ/äooo¹ ¶ �ÒÁÕoieÅ硵o¹·Õèe¤Åèo¹·Õèä»ÁÒoÂ�Ò§oiÊÃa eª�¹¾a¹¸aoÅËa ¡ç¨a¹íÒä¿¿�Òä �
Lecture 6 - Physical Properties of Minerals 11
Magnetic Property
Ferromagnetic � æÁ �eËÅç¡ Ù´µi´ä �Paramagnetic � æÁ �eËÅç¡Ù´Âa§äÁ �µi´ æµ�eÁ èoeoÒä»ãÊ�ã¹
ʹÒÁæÁ �eËÅç¡ ¨a¡ÅÒÂe»�¹æÁ �eËÅç¡o �o¹æ ä´ �Diamagnetic� äÁ �ÊÒÁÒö·íÒãË�e»�¹æÁ �eËÅç¡ä �eÅÂ
e»�¹¤u³ÊÁºaµi·Õè¢ é¹oÂÙ�¡aºª¹i¢o§oaµoÁ/äooo¹ æÅao´Âe©¾Òao �Ò§Âiè§ ¡Òèa´eÃÕ§oieÅ礵Ão¹ã¹ orbitals « 觨a¢ é¹oÂÙ�¡aº magnetic quantum number
Lecture 6 - Physical Properties of Minerals 12
Examples
Ferromagnetic = Magnetite (Fe3O4)Paramagnetic =
Olivine (Mg,Fe)SiO4
Pyroxene (Ca,Na)(Mg,Fe,Al)(Al,Si)2O6
paramagnetic
Lecture 7 - Thermodynamics I 1
ThermodynamicsThermodynamics o u³Ë¾ÅÈÒʵÃ�
Systems vs. SurroundingsIntensive vs. Extensive PropertiesFundamental Laws of Thermodynamics
Lecture 7 - Thermodynamics I 2
e·oÃ�oÁä´¹ÒÁi¡Ê �e¤ÁÕ·íÒäÁ¹éíÒ¡ÅÒÂe»�¹¹éíÒæ¢ç§Ëà o¹éíÒæ¢ç§ÅaÅÒ¡ÅÒÂe»�¹¹éíÒ ÁÕ»�¨ aÂoaäÃÁÒe¡ÕèÂÇ¢ �o§?·íÒäÁ¡Ò÷o´ä¢ �e ÕÂÇ (»¯ i¡ià iÂÒ·Õè·íÒãË�ä¢ �Êu¡) ¨§e»�¹»¯ i¡ià iÂÒ·Õè �o¹¡Å aºäÁ �ä �?·íÒäÁÊÒÃe¤ÁÕºÒ§ª¹i´ÅaÅÒ¹éíÒæÅ �Çou³ËÀÁ i¢o§¹éíÒe»ÅÕè¹ä»e˵uã´æÁ¡ÁÒµaÇe ÕÂÇ¡ a¹ æµ�µ¡¼Å ¡·Õè¤ÇÒÁ´ a¹µ�Ò§¡a¹¨aãË�æà �·ÕèäÁ �eËÁo¹¡a¹?·íÒäÁe¾ªÃ« è§e»�¹¤Òà �ºo¹·ÕèeʶÕÂà ³ ¤ÇÒÁ´ a¹ÊÙ§æ ¨§oÂÙ�º¹¼iÇoÅ¡« è§ÁÕ¤ÇÒÁ´ a¹e¾Õ§ 1 ºÃÃÂÒ¡ÒÈ ä �o´ÂäÁ �e»ÅÕè¹e»�¹æ¡Ã俵�
¤íÒ¶ÒÁeËÅ�Ò¹ÕéÊÒÁÒöµoºä �o´Âãª�ËÅa¡¡Ò÷ҧe·oà �oÁä´¹ÒÁi¡Ê�e¤ÁÕ
Lecture 7 - Thermodynamics I 3
Thermodynamics e¡ÕèÂÇ¢�o§¡ aº¸Ã³ÕÇi·ÂÒo �Ò§äÃ?
¡Òõ¡¼Å ¡¢o§æÁ¡ÁÒe»�¹æà �µ�Ò§æ ¨a¶Ù¡¤Çº¤uÁo´Âo§¤�»Ãa¡oº¢o§æÁ¡ÁÒ (Composition)¾Åa§§Ò¹æÅa¡Òö�ÒÂe·¾Å a§§Ò¹ (Energy)ou³ËÀÙÁ i æÅa¤ÇÒÁ´ a¹ (Temperature & Pressure)
o´Â¨aÁÕ¡Òö�ÒÂe·¾Å a§§Ò¹ÃaËÇ�Ò§Ãaºº¡aºÊiè§æÇ´Å �oÁ ã¹¢³a·ÕèÊÊÒÃÀÒÂã¹Ãaºº¨aÁÕ¡ÒÃe»ÅÕè¹ÃÙ»Ëà oe»ÅÕè¹ʶҹa¡Òüu¾ a§·íÒÅÒ (chemical weathering) ¢o§Ëi¹Ëà oæà �º¹¼iÇoÅ¡ e¡i´¢ é¹e¾ÃÒaoaäÃ? ·íÒäÁæà �ºÒ§µaǶ§¶Ù¡¼u¾ a§·íÒÅÒÂä �§ �Ò 㹢³a·Õèæà �oÕ¡µaÇ˹觨a·¹·Ò¹µ �o¡Òüu¾ a§ÁÒ¡¡Ç �Ò
ãª�o¸ iºÒ �ÊÁ uÅ� e¤ÁÕ
Lecture 7 - Thermodynamics I 4
System vs. Surroundings
Ãaºº »Ãa¡oº´ �ÇÂÊÊÒê¹ i µ�Ò§æ »a»¹¡a¹oÂÙ� ËÒ¡ÊÊÒÃÁÕ¢oºe¢µ·ÕèÁo§eËç¹ä´ �ªa´e¨¹ eÃÒ¨aeÃÕ¡Áa¹Ç �Òe»�¹ phase ˹ è§ «è§ÃaººË¹ è§æ ÁÕä´ �ËÅÒ phase eª�¹ ÃaººoÒ¨»Ãa¡oº´ �Ç æÃ� Ëi¹ ¹éíÒ oÒ¡ÒÈ æÁ¡ÁÒ ÏÅÏ « è§ÊÊÒÃæµ �Åa phase ·ÕèoÂÙ�¡a¹oÂ�Ò§ �ÊÁ´uÅ� ¡ç¨aÁÕÊÒÃe¤ÁÕ·Õè»Ãa¡oº¢é¹ÁҨҡ˹ �ÇÂËÅa¡e¾Õ§˹ è§ËÃoËÅÒÂæ ˹�Ç «è§æµ �Åa˹ �ÇÂeÃÕÂ¡Ç �Ò component
Lecture 7 - Thermodynamics I 5
ª¹i ¢o§ �Ãaºº� ã¹æ§ �¢o§e·oÃ�oÁä´¹ÒÁi¡Ê �
Ãaººe»�´ (open system)ÁÕ¡ÒÃæÅ¡e»ÅÕè¹· aé§ÁÇÅÊÒÃæÅa¾Åa§§Ò¹¡ aºÊiè§æÇ´Å�oÁÃaºº» �´ (closed system)
ÁÕ¡Òö �ÒÂe·¾Åa§§Ò¹e¢ �Ò-oo¡Ãaºº æµ�äÁ�ÁÕ¡Òö �ÒÂe·ÁÇÅÊÒÃÃaººæ¡µ aÇ (isolated system)Ãaºº·ÕèäÁ�ÁÕ¡Òö �ÒÂe·· aé§ÁÇÅÊÒÃËà o¾Åa§§Ò¹
Lecture 7 - Thermodynamics I 6
µ aÇoÂ�Ò§¢o§ �Ãaºº�
Lecture 7 - Thermodynamics I 7
How to describe �system�?
eÇÅÒ¾Ù ¶§Ãaºº eÃÒ¨aãª�µ aÇæ»ÃÁÒo iºÒ « 觵 aÇæ»ÃeËÅ�Ò¹ÕéeÃÕÂ¡Ç �Ò �¿�§¡ �ªa¹º�§Ê¶Ò¹a� Ëà o Function of State « è§e»�¹¤u³ÊÁºaµ ie©¾Òaµ aÇ¢o§Ãaºº ä �æ¡ � ¨íҹǹoÁÅ o u³ËÀÙÁi ¤ÇÒÁ´ a¹ eo ¹·ÒÅ» � eo ¹o·Ã» � ¾Åa§§Ò¹oiÊÃa ¾Åa§§Ò¹ÀÒÂã¹ ÏÅϤu³ÊÁºaµ ieËÅ�Ò¹Õé æº �§oo¡e»�¹Êo§»ÃaeÀ· ä´�æ¡ �
¤u³ÊÁº aµi·Õèe»�¹ Extensive (¢ é¹oÂÙ�¡aº¢¹Ò´¢o§Ãaºº)¤u³ÊÁº aµi·Õèe»�¹ Intensive (äÁ �¢ 鹡aº¢¹Ò´¢o§Ãaºº)
Lecture 7 - Thermodynamics I 8
Intensive Properties
äÁ�¢ 鹡 aº¢¹Ò´¢o§Ãaºº ¡Å�ÒǤo ¶ �ÒÃaººÁÕ¢¹Ò´ãË�¢ é¹ Ëà oÁջà iÁÒ³ÊÒÃÁÒ¡¢ é¹ ¨aÁÕ¤u³ÊÁºaµ ieËÅ�Ò¹Õé¡ç aäÁ�e»ÅÕèÂ¹ä» eÃÒeÃÕÂ¡Ç �Ò äÁ�ÁÕ¤u³ÊÁºaµ i溺 additiveeª�¹ o u³ËÀÙÁi¢o§Ãaºº ¨aäÁ�ãª�o u³ËÀÙÁi¢o§·u¡æ ÊÊÒÃã¹ÃaººÃÇÁ¡ a¹Ëà o ¤ÇÒÁe¢ �Á¢ �¹¢o§e¡Åoã¹ÊÒÃÅaÅÒ ¨aÁÕ¤ �Ò¤§·Õè äÁ�Ç �ÒÊÒÃÅaÅÒ¹ aé¹æ ¨aÁÕ¶Ù¡æº �§oo¡ä»ãË�Áջà iÁÒ³·Õè浡µ �Ò§¡ a¹
Lecture 7 - Thermodynamics I 9
Extensive Properties
¢ 鹡 aº¢¹Ò´¢o§Ãaºº ¡Å�ÒǤo ¶ �ÒÃaººÁÕ¢¹Ò´ãË�¢ é¹ Ëà oÁջà iÁÒ³ÊÒÃÁÒ¡¢ é¹ ¨aÁÕ¤u³ÊÁºaµ ieËÅ�Ò¹Õée¾ ièÁ¢ é¹ eÃÒeÃÕÂ¡Ç �ÒÁÕ¤u³ÊÁºaµ i溺 additive (ºÇ¡)eª�¹ ¨íҹǹoÁÅ¢o§¸Òµuo«e´ÕÂÁã¹Ãaºº ¨ae· �Ò¡ aº¨íҹǹ oÁÅ¢o§¸Òµuo«e´ÕÂÁã¹æµ �Åa phase ÃÇÁ¡ a¹Ëà o »Ã iÁÒ³¾Åa§§Ò¹ÀÒÂã¹Ãaºº ¨ae· �Ò¡ aº ¾Åa§§Ò¹ÀÒÂã¹¢o§æµ �ÅaÊÊÒÃã¹ÃaººÃÇÁ¡ a¹ e»�¹µ �¹
Lecture 7 - Thermodynamics I 10
Example of Properties
Mole (n)Volume (V)Internal Energy (E)Enthalpy (H)Gibbs Free Energy (G)
Temperature (T)Pressure (P)Concentration (C)Chemical Potential (μ)
EXTENSIVE INTENSIVE
Lecture 7 - Thermodynamics I 11
µ aÇo �Ò§¡ÒÃ㪠�¿ �§¡ �ª a¹º �§Ê¶Ò¹a (Function of State)
= ( , )V f T P
=
∂ ∂⎛ ⎞ ⎛ ⎞= +⎜ ⎟ ⎜ ⎟∂ ∂⎝ ⎠ ⎝ ⎠
( , )
P T
V f T P
V VdV dT dPT P
=nRTVP
»ÃiÁҵâo§æ¡ �Êã¹·�oÊÙº¢é¹oÂÙ�¡ aºo u³ËÀÙÁiæÅa¤ÇÒÁ a¹
eÃÒoÂÒ¡·ÃÒºÇ �Ò æ¡ �Êã¹o u Á¤µi (PV=nRT) ¨íҹǹ n oÁŨaÁÕ»ÃiÁÒµÃe»ÅÕè¹ä»e·�Òã´ ¶ �Ò¤ÇÒÁ a¹æÅao u³ËÀÙÁie»ÅÕèÂ¹ä» ΔP æÅa ΔT µÒÁÅíÒ aº
2
P
T
V nRT PV nRTP P
∂⎛ ⎞ =⎜ ⎟∂⎝ ⎠∂⎛ ⎞ = −⎜ ⎟∂⎝ ⎠
= −
Δ ≈ Δ − Δ
2
2
nR nRTdV dT dPP PnR nRTV T PP P
Lecture 7 - Thermodynamics I 12
µ aÇoÂ�Ò§¿ �§¡ �ª a¹º�§Ê¶Ò¹a (Function of State)
=
=
=
= ×
Δ = +
Δ = −
-1 -1
5 -2
-2
1 mol
8.3143 J mol K
298 K
1.01325 10 N m
30 K
5,000 N m
n
R
T
P
T
P
Δ ≈ Δ − Δ2
nR nRTV T PP P
¶ �Òæ¡ �Êã¹o u´Á¤µi 1 oÁÅã¹Ãaºº» �´ (e iÁÁÕo u³ËÀÙÁi 298 K æÅa¤ÇÒÁa¹ 1.01325×105 N/m2) ÁÕo u³ËÀÙÁie¾ ièÁ¢é¹ 30 K æÅa¤ÇÒÁ a¹
Ŵŧ 5,000 N/m2 ¨§¤íҹdzËÒ»ÃiÁҵâo§æ¡ �Ê·Õèe»ÅÕè¹ä»
−
Δ ≈ + − −× ×
= + ×
= +
5 5 2
3 3
(1)(8.3143) (1)(8.3143)(298)( 30) ( 5000)1.01325 10 (1.01325 10 )3.67 10 m
3.67 L
V
æ¡ �ʨaÁջà iÁÒµÃe¾ ièÁ¢ é¹ 3.67 ÅiµÃ
Lecture 7 - Thermodynamics I 13
Laws of Thermodynamics
Zeroth LawThermodynamic Equilibrium (¶ �ÒÃaººÊo§ÃaººoÂÙ�µ i´¡ a¹æÅaÁÕo u³ËÀÙÁie· �Ò¡ a¹ eÃÕÂ¡Ç �ÒoÂÙ�ã¹ÊÀÒÇaÊÁ´uÅ·Ò§e·oà �oÁä´¹ÒÁi¡Ê� « 觻Ãa¡oº´ �ÇÂÊÁ´uÅ· aé§ÊÒÁ溺
Thermal EquilibriumMechanical EquilibriumChemical Equilibrium
Lecture 7 - Thermodynamics I 14
Laws of Thermodynamics
First LawConservation of Energy ËÃo¡®o¹uà a¡É�¾Åa§§Ò¹ « 觡Å�ÒÇÇ �Ò ¾Åa§§Ò¹ÀÒÂã¹Ãaºº·Õèe»ÅÕè¹æ»Å§ä» (dE) ¨ae· �Ò¡ aº¾Åa§§§Ò¹¤ÇÒÁà �o¹·ÕèÃaºº´Ù e¢ �Òä»Ëà o¤ÒÂoo¡ÁÒ (dQ) ºÇ¡¡ aº»Ã iÁÒ³§Ò¹·ÕèÃaºº·Õè¡Ãa·íÒµ �oËà o¶Ù¡¡Ãa·íÒo´ÂÊiè§æÇ´Å�oÁ (dW)
dE = dQ - dWÃaºº·íÒ§Ò¹ dW ÁÕe¤Ãèo§ËÁÒÂe»�¹ �ºÇ¡�Ãaºº Ù´¤ÇÒÁÃ�o¹ dQ ÁÕe¤Ãèo§ËÁÒÂe»�¹ �ºÇ¡�ÃaººÁÕ¾Åa§§Ò¹ÀÒÂã¹e¾ ièÁ¢é¹ dE ¨aÁÕ¤�Òe»�¹ �ºÇ¡�
dW = PdV
Lecture 7 - Thermodynamics I 15
Laws of Thermodynamics
Second Law ¡®·Õèe¡ÕèÂÇ¡aº¤ÇÒÁäà �ÃaeºÕº¢o§Ãaºº « 觤ÇÒÁäà �ÃaeºÕº¹Õé ºo¡ä � �ÇȈ iÁÒ³·ÕèeÃÕÂ¡Ç �Ò �eo ç¹o·Ã» �� (Entropy, S)
ÃaººæÅaÊiè§æÇ´Å�oÁ ¨a¾ÂÒÂÒÁ´íÒe¹ i¹ä»ã¹·iÈ·Ò§·Õèe¾ ièÁ¤ÇÒÁäÁ�e»�¹ÃaeºÕº Ëà oe¾ ièÁeo ç¹o·Ã» �
ΔStotal = ΔSsys + ΔSsurr ≥ 0
Lecture 7 - Thermodynamics I 16
Entropy, S
㹡ÃaºÇ¹¡ÒÃËà o» i¡ ià iÂÒ·Õè¼a¹¡Åaºä´ �: ¡ÒÃe»ÅÕè¹æ»Å§eo ç¹o·Ã» �e· �Ò¡ aº¤ÇÒÁà �o¹·Õè¶ �ÒÂe·e¢ �Ò-oo¡¨Ò¡ÃaººËÒô �ÇÂo u³ÀÙÁiÊaÁºÙó�
㹡ÃaºÇ¹¡ÒÃËà o» i¡ ià iÂÒ·Õè¼a¹¡ÅaºäÁ�ä´ � (« 觻 i¡ ià iÂÒËà o¡ÃaºÇ¹¡ÒÃÊ�ǹãË� ae»�¹æºº¹Õé)
dS = dQ/T
dS ≥ dQ/T
Lecture 7 - Thermodynamics I 17
Laws of Thermodynamics
Third Law ³ o u³ËÀÙÁ i 0 K (e¤ÅÇ i¹) ¡ÃaºÇ¹¡Ò÷u¡oÂ�Ò§ËÂu´ËÁ´ æÅa¤ �Òeo ¹o·Ã» � (S) ËÃo¤ÇÒÁäà �ÃaeºÕº¢o§ÃaººÁÕ¤ �Òe» �¹ÈÙ¹Â�
ST = 0 K = 0
�eo ç¹o·Ã»�� e»�¹ extensive properties e¾Õ§ª¹ i´e ÕÂÇã¹·Ò§e·oà �oÁä´¹ÒÁi¡Ê�·ÕèÊÒÁÒöËÒ¤ �Òä � Ê�ǹ»Ã iÁÒ³o è¹æ ¹ aé¹ËÒ¤ �Òä �e¾Õ§ ¤ÇÒÁe»ÅÕè¹æ»Å§Ëà o Δ eª�¹ ΔQ, ΔE
Lecture 8 - Thermodynamics II 1
ThermodynamicsThermodynamics o u³Ë¾ÅÈÒʵÃ�
Heat of Reaction/Transformation (Q)Heat Capacity (Cp or Cv)Enthalpy (H)
e¹ �¹e©¾Òa·Õè¨a¹íÒÁÒãª�¡ aº¸Ã³ÕÇ i·ÂÒ
Lecture 8 - Thermodynamics II 2
Heat Exchange due to Reaction or Transformation (Q)
¤ÇÒÁà �o¹·ÕèÁÕ¡Òö �ÒÂe·e¢ �Ò-oo¡¨Ò¡Ãaºº æÅ�Ç·íÒãË�e¡ i¡ÒÃe»ÅÕè¹æ»Å§ eª�¹¡ÒÃe»ÅÕè¹æ»Å§Ê¶Ò¹a¨Ò¡¢o§æ¢ç§ä»e»�¹¢o§eËÅÇ Ëà o¤ÇÒÁà �o¹·Õè¶ �ÒÂe·e¢ �Ò-oo¡Ãaºº« 觷íÒãË�o u³ËÀÙÁi¢o§Ãaººe»ÅÕè¹仫 觻à iÁÒ³¤ÇÒÁà �o¹¹ÕéÊÒÁÒö �Ç a � ä´ � Ëà o ÊÒÁÒö¤íÒ¹Ç³ä´ � Ò¡¤ÇÒÁà �o¹¨íÒe¾Òa (Heat Capacity, C)
Lecture 8 - Thermodynamics II 3
Heat Capacity (C)
¤ÇÒÁà �o¹¨íÒe¾Òa = »Ã iÁÒ³¤ÇÒÁà �o¹ (µ �ooÁÅ) ·Õè¶ �ÒÂe·e¢ �Ò-oo¡¨Ò¡Ãaºº æÅ�Ç·íÒãË�ÊÊÒÃÁÕo u³ËÀÙÁie»ÅÕèÂ¹ä» 1 K
¶ �Òo u³ËÀÙÁi¢o§ÊÒÃe»ÅÕèÂ¹ä» æµ �»Ã iÁҵà (V) äÁ�e»ÅÕè¹
¶ �Òo u³ËÀÙÁi¢o§ÊÒÃe»ÅÕèÂ¹ä» æµ �¤ÇÒÁ´ a¹ (P) äÁ�e»ÅÕè¹
C = dQ/dT
Cv = dE/dT
Cp = dH/dT
สตรทวไป
ทางธรณวทยาสวนใหญจะใช Cp
Lecture 8 - Thermodynamics II 4
Heat Capacity (C)
¤ÇÒÁÊaÁ¾ a¹ �ÃaËÇ �Ò§ Cp æÅa CV
o´Â»¡µ iæÅ�Ç ¤ �Ò Cp ¨a¢ é¹oÂÙ�¡ aºo u³ËÀÙÁi (T)
Cp = CV + TVα2/β
Cp = a + bT + cT-2 + dT-0.5
α = สมประสทธการขยายตวเนองจากความรอนβ = สมประสทธการถกบบอดเนองจากความดน
㹡óբo§æ¡ �Êã¹ou´Á¤µi Cp = CV + R
Cp = a + bT - cT-2หรอ
Lecture 8 - Thermodynamics II 5
Enthalpy (H)
ËÁÒ¶§¾Å a§§Ò¹¤ÇÒÁà �o¹·ÕèÊaÊÁoÂÙ�ã¹o¤Ã§Ã �Ò§¼Å ¡
o´Â»¡µiæÅ �Ç ¤ �Òeoç¹·ÒÅ»� (H) ¨aËÒ¤ �ÒäÁ �ä � eÃÒËÒä �e¾Õ§¤ÇÒÁe»ÅÕè¹æ»Å§¢o§eoç¹·ÒÅ»�Ëà o ΔH eª �¹
¡ÒÃe»ÅÕè¹æ»Å§¢o§eoç¹·ÒÅ» � (¾Åa§§Ò¹·Õè Ù´ËÃo¤ÒÂ) ¨Ò¡» i¡iÃiÂÒe¤ÁÕ ³ ou³ËÀÙÁ i¤§·Õè¡ÒÃe»ÅÕè¹æ»Å§¢o§eoç¹·ÒÅ» � (¾Åa§§Ò¹·Õè Ù´ËÃo¤ÒÂ) ¨Ò¡¡ÒÃe»ÅÕè¹æ»Å§·Õèou³ËÀÙÁ iäÁ �¤§·Õè
H = E + PV
Lecture 8 - Thermodynamics II 6
¡ÒÃe»ÅÕè¹æ»Å§¢o§eo ç¹·ÒÅ» � ΔH
㹡óշÕèo u³ËÀÙÁi �¤§·Õè� ËÒä �¨Ò¡eo ç¹·ÒÅ» �¢o§¡ÒÃe¡ i
㹡óշÕèo u³ËÀÙÁiäÁ�¤§·Õè ¨aµ �o§ãª�¤ �Ò Cp ÁÒª �ǤíҹdzΔHf
o ËÁÒ¶§eo ç¹·ÒÅ» �¢o§¡ÒÃe¡i´ (Enthalpy of Formation)
2
1 2
1
T
T T pT
H H H C dTΔ = − = ∫สาหรบกรณทความดนคงท
ΔHr = Σ(ΔHfo)products � Σ(ΔHf
o)reactants
Lecture 8 - Thermodynamics II 7
µ aÇoÂ�Ò§¡Òäíҹdzeo ç¹·ÒÅ» �
¨§¤íҹdzËÒ¤ �Òeo ç¹·ÒÅ» �·Õèe»ÅÕè¹æ»Å§ä» (Ëà o¾Åa§§Ò¹¤ÇÒÁà �o¹·Õè¶ �ÒÂe·e¢ �Ò-oo¡Ãaºº) eÁèoãË�¤ÇÒÁà �o¹æ¡ �æà �¤Çoµ« �¨¹ÁÕo u³ËÀÙÁie¾ ièÁ¢ 鹨ҡ 298 K e»�¹ 1000 K
¨§¤íҹdzËÒ¤ÇÒÁà �o¹¢o§» i¡ ià iÂÒe¤ÁÕµ �o仹Õé ³ 298 K2H2S(g) + 3O2(g) ↔ 2H2O(l) + 2SO2(g)
Lecture 8 - Thermodynamics II 8
EX 1: eo¹·ÒÅ» �·Õèe»ÅÕè¹æ»Å§ eÁèoou³ËÀÙÁiäÁ�¤§·Õè
¨§¤íҹdzËÒ¤ÇÒÁà �o¹·ÕèãË�æ¡�æà �¤Çoµ« � íҹǹ 1 mol e¾ èoãË�ou³ËÀÙÁ ie¾ ièÁ¢ 鹨ҡ 298 K e»�¹ 1000 K
µaÇæ»Ã ¤�Òa 104.35
b 6.07x10-3
c 3.4x10-4
d -1070
¡íÒ˹´ãË�
( ) ( )
( )
2
1
2
1
2 0.52 1
10002
298
2 2
-1
22
1000 298 1000 2982
1 1 2 1000 2981000 298
45.37 kJ mol
T
T
T
T
H H H a bT cT dT dT
b cH aT T d TTba
c d
H
− −
=
=
− = Δ = + + +⎡ ⎤⎣ ⎦
⎡ ⎤Δ = + − +⎢ ⎥⎣ ⎦
= − + −
⎛ ⎞− − + −⎜ ⎟⎝ ⎠
Δ =
∫
Cp = a + bT + cT-2 + dT-0.5
2 2
1 1
p
H T
pH T
dH C dT
dH C dT
=
=∫ ∫
µ �o§ãË �¤ÇÒÁà �o¹e»�¹»ÃiÁÒ³ 45.37 kJ ¨§¨a·íÒãË �æÃ�¤Çoµ«�íҹǹ 1 oÁÅ ÁÕo u³ËÀÙÁ ie¾ ièÁ¨Ò¡ 298 K e»�¹ 1000 K
Cp = dH/dT
Lecture 8 - Thermodynamics II 9
EX 2: eo¹·ÒÅ» �·Õèe»ÅÕè¹æ»Å§ ³ ou³ÀÙÁi¤§·Õè
¨§¤íҹdzËÒ¤ÇÒÁà �o¹¢o§» i¡ ià iÂÒe¤ÁÕµ �o仹Õé ³ 298 K2H2S(g) + 3O2(g) ↔ 2H2O(l) + 2SO2(g)
ΔHr = Σ(ΔHfo)products � Σ(ΔHf
o)reactants Compound ΔHof
(kJ/mol)
H2S (g) -20.6
O2 (g) 0
H2O (l) -285.8
SO2 (g) -296.8
¨Ò¡µÒÃÒ§
[ ] [ ]2( 285.8) 2( 296.8) 2( 20.6) 3(0)
1124 kJrHΔ = − + − − − +
= −
³ o u³ËÀÙÁi 298 K » i¡ iÃiÂÒe¤ÁÕã¹Ãaºº¢�Ò§µ�¹¨aÁÕeo ç¹·ÒÅ» �Ŵŧ (ËÃo¤Ò¤ÇÒÁà �o¹) e·�Ò¡ aº 1124 kJ
Lecture 8 - Thermodynamics II 10
ΔH = �+�
e¤Ãèo§ËÁÒ¢o§ ΔH
ระบบจะดดความรอนเขาไปในตวมน ซงเรยกปฏกรยาหรอการเปลยนแปลงแบบนวา Endothermic reaction/transformation
ΔH = �−� ระบบจะคายความรอนใหกบสงแวดลอม ซงเรยกปฏกรยาหรอการเปลยนแปลงแบบนวา Exothermic reaction/transformation
Lecture 9 - Thermodynamics III 1
ThermodynamicsThermodynamics o u³Ë¾ÅÈÒʵÃ�
Constant Pressure Heat Capacity (Cp)Enthalpy (H)Entropy (S)Gibbs Free Energy (G)Molar Volume (V)
e¹ �¹e©¾Òa·Õè¨a¹íÒÁÒãª�¡ aº¸Ã³ÕÇ i·ÂÒ
Lecture 9 - Thermodynamics III 2
ΔH ·Õèe»ÅÕè¹æ»Å§ä»¢o§»¯ i¡ ià iÂÒ·Õèou³ËÀÙÁioè¹æ
eª �¹ oÂÒ¡·ÃÒºÇ �Ò ¨aÁվŠa§§Ò¹¤ÇÒÁà �o¹¶�ÒÂe·e·�Òã´ ¶�Ò»¯ i¡ià iÂÒe¤ÁÕµ�o仹Õé « è§e¡i´·Õèou³ËÀÙÁ i 1000 K?
㹡óÕeª �¹¹Õé ¨a㪠�µÒÃÒ§¤ �Òe·oà �oÁä´¹ÒÁ i¡Ê�e¾Õ§o �Ò§e ÕÂÇäÁ �ä � e¾ÃÒaµÒÃÒ§¨aÁÕe©¾Òa¤�Ò ΔHo
f ³ 298 K e·�Ò¹aé¹ ¨aµ�o§ãª � heat capacity (Cp) ÁÒe¡ÕèÂÇ¢ �o§
Si(s) + O2(g) ↔ SiO2(s)
Lecture 9 - Thermodynamics III 3
µaÇæ»Ã SiO2 Si O2
31.778 48.318
-6.91x10-4
4.99x105
d -1070 -178.6 -420.7
ΔHfo (kJ/mol) -910.9 0 0
5.39x10-4
-1.47x105
a 104.35
b 6.07x10-3
c 3.4x10-4
¢�oÁÙÅ·Õè¡íÒ˹´ãË�
− −= + + +2 0.5PC a bT cT dT
Lecture 9 - Thermodynamics III 4
Çi Õ·íÒ: ¢aé¹·Õè 1 ¤íҹdzËÒ¤ �Ò ΔHro
ΔHro = Σ(ΔHf
o)products � Σ(ΔHfo)reactants
⎡ ⎤ ⎡ ⎤Δ = Δ − Δ + Δ⎣ ⎦ ⎣ ⎦= − − += −
o o o o
2 2r f ,SiO f ,Si f ,Oproduct reactantH H H H
( 910.9) (0 0)
910.9 kJ
¤�Ò·Õèä �¤oeo ç¹·ÒÅ»�¢o§» i¡ iÃiÂÒ ³ ÊÀÒÇaÁҵðҹ (T=298 K, P=1 atm)
Lecture 9 - Thermodynamics III 5
Çi Õ·íÒ: ¢aé¹·Õè 2 ¤íҹdzËÒ¤ �Ò ΔCP
− −Δ = Δ + Δ + Δ + Δ2 0.5PC a bT cT dT
( ) ( ) ( )Δ = −∑ ∑P P Pr product reactantC C C
[ ] [ ]
( )( )
[ ] ( ) ( )[ ]
− − − −
−
Δ = − + =
⎡ ⎤Δ = × − × + − × = ×⎡ ⎤⎣ ⎦ ⎣ ⎦
⎡ ⎤Δ = × − − × + × = − ×⎡ ⎤⎣ ⎦ ⎣ ⎦Δ = − − − + − = −
prod reac
3 4 4 3
prod reac
4 5 5 5
prod reac
prod reac
a 104.35 31.778 48.318 24.254
b 6.07 10 5.39 10 6.91 10 6.222 10
c 3.40 10 1.47 10 4.99 10 3.52 10
d 1070 178.6 420.7 470.7
โดยคาสมประสทธตางๆ คานวณไดดงน
Lecture 9 - Thermodynamics III 6
Çi Õ·íÒ: ¢aé¹·Õè 3 ¤íҹdzËÒ¤ �Ò ΔHr( )
( )Δ
Δ
Δ = Δ
Δ = Δ∫ ∫T 2 2
T 1 1
P
H T
PH T
d H C dT
d H C dTΔ = Δ + Δ∫
2
2 1
1
T
T T PT
H H C dT
− −Δ = Δ + Δ + Δ + Δ2 0.5PC a bT cT dT
( ) ( )
( )
=
==
=− −
==
=
= Δ + Δ
= Δ + Δ + Δ + Δ + Δ⎡ ⎤⎣ ⎦
Δ Δ⎡ ⎤= Δ + Δ + − + Δ⎢ ⎥⎣ ⎦Δ⎧ ⎫Δ − + −⎪ ⎪⎪ ⎪= Δ + ⎨ ⎬
⎛ ⎞⎪ ⎪−Δ − + Δ −⎜ ⎟⎪ ⎪⎝ ⎠⎩ ⎭
∫
∫
T 1000
r ,T 298 PT 298
T 1000o 2 0.5r
T 298
T 1000o 2r
T 298
2 2
or
H C dT
H a bT cT dT dT
b cH aT T 2 d T
2 Tb
a 1000 298 1000 2982H
1 1c 2 d 1000 298
1000 298
˹ �Ç¢o§ CP ¤ o J mol-1 K-1
˹ �Ç¢o§ ΔCP ¤o J K-1
˹ �Ç¢o§ ∫ΔCP ¤o J
=Δ r ,T 1000H
Lecture 9 - Thermodynamics III 7
Çi Õ·íÒ: ¢aé¹·Õè 3 ¤íҹdzËÒ¤ �Ò ΔHr (µ�o)( ) ( )
( )=
Δ⎧ ⎫Δ − + −⎪ ⎪⎪ ⎪Δ = Δ + ⎨ ⎬⎛ ⎞⎪ ⎪−Δ − + Δ −⎜ ⎟⎪ ⎪⎝ ⎠⎩ ⎭
= − += − += −
2 2
T 1000 or r
ba 1000 298 1000 298
2H H1 1
c 2 d 1000 2981000 298
910.9 kJ 5513.232 J
910.9 kJ 5.51 kJ
905.39 kJ
a§¹aé¹ » i¡ iÃiÂÒ¡ÒÃe¡ i´æÃ�¤Çoµ«�·Õè 1000 K (1.0 atm) ¨aÁÕ¡ÒäÒ¾Ša§§Ò¹oo¡ÁÒ 905.4 kJ (eo ç¹·ÒÅ» �Ŵŧ)
−
Δ =
Δ = ×
Δ = − ×
Δ = −
3
5
a 24.254
b 6.222 10
c 3.52 10
d 470.7
Lecture 9 - Thermodynamics III 8
Entropy, S
¡ÒÃe»ÅÕè¹æ»Å§ã´æ ·ÕèÁÕ¡Òö �ÒÂe·¤ÇÒÁà �o¹e¢ �Ò-oo¡¨Ò¡Ãaºº ¨aÁÕ¡ÒÃe»ÅÕè¹æ»Å§¢o§eo ç¹o·Ã» � �ÇÂeÊÁoeª�¹ ¹éíÒe»ÅÕè¹ʶҹa » i¡ ià iÂÒe¤ÁÕ¢o§æÁ¡ÁÒ¡ aºæà � ¡Òüu¾ a§·íÒÅÒ¢o§æà � ÏÅÏ
⎧= = ⎨
⎩
P
V
C dT T for constant pressuredQdS
C dT T for constant volumeT Ê �ǹãË�¨a㪠�ÊÁ¡Ò÷ÕèÁÕ Cp
Lecture 9 - Thermodynamics III 9
¡. ¡ÒÃe»ÅÕè¹æ»Å§eo ç¹o·Ã» �eÁèoÁÕ¡ÒÃe»ÅÕè¹ʶҹa
¹éíÒe»ÅÕè¹ʶҹa¨Ò¡¹éíÒ¡ÅÒÂe»�¹äo (·Õè¤ÇÒÁ´ a¹ P = 1.0 atm)¨aÁÕeoç¹o·Ã»�e»ÅÕè¹ä»e·�Òã´? H2O(l) ↔ H2O(g)
Δ= =
Δ + ×Δ = =
= +
r
3r
r
dQ d( H )dS
T TH 40.67 10 J
ST 373.15 K109 J/K
e¹ èo§¨Ò¡¹éíÒ¡ÅÒÂe»�¹äo·Õèou³ËÀÙÁi¤§·Õè (373.15 K) a§¹ aé¹ ¢�o¹ÕéäÁ�¨íÒe»�¹µ�o§oi¹· ie¡Ãµ e¾ÕÂ§æ¤ �·ÃÒº¤ÇÒÁà �o¹æ½§¢o§¡ÒáÅÒÂe»�¹äo¢o§¹éíÒ (¾Å a§§Ò¹¤ÇÒÁÃ�o¹·Õè¹éíÒ´Ù e¢�Òä»æÅ �ÇÃaeË¡ÅÒÂe»�¹äo) «è§ÁÕ¤ �Òe· �Ò¡ aº 40.67 kJ/mol
¹a蹤o eÁèo¹éíÒä �Ãaº¤ÇÒÁÃ�o¹¨¹¡ÅÒÂe» �¹äo (·Õèo u³ËÀÙÁi¤§·Õè 373.15 K, 1.0 atm) Ãaºº¨aÁÕeo ç¹o·Ã» �e¾ ièÁ¢é¹ 109 J/K ¹aè¹
¤o Ãaºº¨aÁÕ¤ÇÒÁäÃ�ÃaeºÕºe¾ ièÁ¢é¹
Lecture 9 - Thermodynamics III 10
¢. ¡ÒÃe»ÅÕè¹æ»Å§eo ç¹o·Ã»�㹡óշÕèo u³ËÀÙÁie¾ièÁ¢é¹ æµ�äÁ�e¡ i » i¡ iÃiÂÒe¤ÁÕ
¨§¤íҹdzËÒeoç¹o·Ã»�¢o§æà �¤Çoµ« � 1.0 mol eÁ èoä �à aº¤ÇÒÁà �o¹¨¹ÁÕou³ËÀÙÁ ie¾ ièÁe»�¹e»�¹ 1000 K
ãª�¹iÂÒÁ¢o§eo ç¹o·Ã» � (dS = CpdT/T)ãª�µÒÃÒ§ËÒ¤ �Ò So ³ o u³ËÀÙÁi·ÕèeÃÒ·ÃÒº
Cp = a + bT + cT-2 + dT-0.5T2
T 1
2
2 1
1
S T2P P
S T1
TP
T TT
C CdS dT dS dT
T T
CS S dT
T
= → → =
− =
∫ ∫
∫
L
เลอก T1 = 298 K, So = 41.8 J/Kให T2 = 1000 K, แลวคานวณหา ST2
Lecture 9 - Thermodynamics III 11
Ç i¸Õ·íÒ: (µ �o)
µaÇæ»Ã ¤�Òa 104.35
b 6.07x10-3
c 3.4x10-4
d -1070
¡íÒ˹´ãË�
Cp = a + bT + cT-2 + dT-0.5
( ) ( )
2
2 1
1
2
TP
T TT
1000 2 0.5
T298
10003 1.5
1000K298
1000
2298
2 2
CS S dT
T
[a bT cT dT ]S 41.8 dT
T
aS 41.8 b cT dT dT
T
c 2d41.8 a ln T bT
2T T41.8 a ln 1000 ln 298 b 1000 298
c 1 1 1 12d
2 1000 298 1000 298
− −
− −
− =
+ + +− =
⎡ ⎤= + + + +⎢ ⎥⎣ ⎦
⎡ ⎤= + + − −⎢ ⎥⎣ ⎦= + − + −
⎛⎛ ⎞− − − −⎜ ⎟⎝ ⎠ ⎝
∫
∫
∫
41.8 74.3 116.1 J/K
⎞⎜ ⎟
⎠= + = Sqtz, 1000K = 116.1 J/K
Lecture 9 - Thermodynamics III 12
¤. ¡ÒÃe»ÅÕè¹æ»Å§eo ç¹o·Ã» �㹡óշÕèe»�¹»¯ i¡ià iÂÒe¤ÁÕ
µ�o§¡Ò÷ÃÒº¤ �Òeoç¹o·Ã»�·Õèe»ÅÕè¹仢o§»¯ i¡ià iÂÒ (ΔSr) µ�o仹Õé ³ ou³ËÀÙÁ i 298 K æÅa 1000 K (·Õè¤ÇÒÁ´ a¹ P = 1.0 atm)
¡Ã³Õeª�¹¹Õé ¨a¤Å �Ò¡ aº¡Ã³Õ¢o§eo ç¹·ÒÅ» �·Õèe¾ i觨a¤íÒ¹Ç³ä» «è§¡ �o¹o è¹µ�o§ãª�¤�Ò¨Ò¡µÒÃÒ§e·oÃ�oÁä´¹ÒÁ i¡Ê �ËÒ¤�Ò¢o§
ΔSro (·ÕèÊÀÒÇaÁҵðҹ) eÊÕ¡ �o¹ æÅ �Ǩ§ãª�¹iÂÒÁ¢o§eo ç¹
o·Ã» �e¾ èoËÒ¤�Ò ΔSr ·Õèo u³ËÀÙÁiÊÙ§¢é¹µ�oä»
Si(s) + O2(g) ↔ SiO2(s)
Lecture 9 - Thermodynamics III 13
µaÇæ»Ã SiO2 Si O2
31.778 48.318
-6.91x10-4
4.99x105
d -1070 -178.6 -420.7
So (J/mol-K) 41.8 18.8 205.1
5.39x10-4
-1.47x105
a 104.35
b 6.07x10-3
c 3.4x10-4
¢�oÁÙÅ·Õè¡íÒ˹´ãË�
− −= + + +2 0.5PC a bT cT dT
Lecture 9 - Thermodynamics III 14
Çi Õ·íÒ: ¢aé¹·Õè 1 ¤íҹdzËÒ¤ �Ò ΔSo
ΔSro = Σ(So)products � Σ(So)reactants
2 2r SiO Si Oproduct reactantS S S S
(41.8) (18.8 205.1)
182.1 J/K
⎡ ⎤ ⎡ ⎤Δ = − +⎣ ⎦ ⎣ ⎦= − += −
o o o o
¤�Ò·Õèä �¤oeo ç¹o·Ã»�¢o§» i¡ iÃiÂÒ ³ ÊÀÒÇaÁҵðҹ (T=298 K, P=1 atm)
Lecture 9 - Thermodynamics III 15
Çi Õ·íÒ: ¢aé¹·Õè 2 ¤íҹdzËÒ¤ �Ò ΔCP
− −Δ = Δ + Δ + Δ + Δ2 0.5PC a bT cT dT
( ) ( ) ( )Δ = −∑ ∑P P Pr product reactantC C C
[ ] [ ]
( )( )
[ ] ( ) ( )[ ]
− − − −
−
Δ = − + =
⎡ ⎤Δ = × − × + − × = ×⎡ ⎤⎣ ⎦ ⎣ ⎦
⎡ ⎤Δ = × − − × + × = − ×⎡ ⎤⎣ ⎦ ⎣ ⎦Δ = − − − + − = −
prod reac
3 4 4 3
prod reac
4 5 5 5
prod reac
prod reac
a 104.35 31.778 48.318 24.254
b 6.07 10 5.39 10 6.91 10 6.222 10
c 3.40 10 1.47 10 4.99 10 3.52 10
d 1070 178.6 420.7 470.7
โดยคาสมประสทธตางๆ คานวณไดดงน
Lecture 9 - Thermodynamics III 16
Çi Õ·íÒ: ¢aé¹·Õè 3 ¤íҹdzËÒ¤ �Ò ΔSr
( )
( )Δ
Δ
ΔΔ =
ΔΔ =∫ ∫
T 2 2
T 1 1
P
S TP
S T
Cd S dT
T
Cd S dT
T
ΔΔ = Δ + ∫
2
2 1
1
TP
T TT
CS S dT
T− −Δ = Δ + Δ + Δ + Δ2 0.5
PC a bT cT dT
( ) ( )
=
= ==
− −=
==
=
ΔΔ = Δ +
Δ + Δ + Δ + Δ⎡ ⎤⎣ ⎦= Δ +
Δ Δ⎡ ⎤= Δ + Δ + Δ − −⎢ ⎥⎣ ⎦Δ − + Δ −
= Δ + Δ ⎛ ⎞⎛ ⎞− − − Δ −⎜ ⎟ ⎜ ⎟⎝ ⎠ ⎝ ⎠
∫
∫
T 1000P
r ,T 1000 r ,T 298T 298
2 0.5T 1000or
T 298
T 1000or 2
T 298
or
2 2
CS S dT
T
a bT cT dTS dT
T
c 2 dS a ln T bT
2T T
a ln 1000 ln 298 b 1000 298
S c 1 1 1 12 d
2 1000 298 1000 298
⎧ ⎫⎪ ⎪⎨ ⎬⎪ ⎪⎩ ⎭
Lecture 9 - Thermodynamics III 17
Çi Õ·íÒ: ¢aé¹·Õè 3 ¤íҹdzËÒ¤ �Ò ΔHr (µ�o)
( ) ( )=
Δ − + Δ −⎧ ⎫⎪ ⎪Δ = Δ + Δ⎨ ⎬⎛ ⎞⎛ ⎞− − − Δ −⎜ ⎟ ⎜ ⎟⎪ ⎪⎝ ⎠ ⎝ ⎠⎩ ⎭
= − += −
T 1000 or r
2 2
a ln 1000 ln 298 b 1000 298
S S c 1 1 1 12 d
2 1000 298 1000 298182.1 J/K 7.16 J/K
174.94 kJ
a§¹aé¹ » i¡ iÃiÂÒ¡ÒÃe¡ i´æÃ�¤Çoµ«�·Õè 1000 K (1.0 atm) ¨aÁÕeo ç¹o·Ã» �Ŵŧ 174.94 J/K « è§o´ÂÃÇÁæÅ �Ç·Õè 1000 K  a§¤§ÁÕeo ç¹o·Ã» �ÊÙ§¡Ç�Ò·Õè 298 K
−
Δ =
Δ = ×
Δ = − ×
Δ = −
3
5
a 24.254
b 6.222 10
c 3.52 10
d 470.7
Lecture 9 - Thermodynamics III 18
eo ç¹·ÒÅ» �·Õèe»ÅÕè¹æ»Å§¢o§»¯ i¡ià iÂÒ ¨ae»�¹µ aǺ �§ºo¡Ç �Ò eÁèoe¡i´» i¡ià iÂÒæÅ �Ç Ãaºº¨aÁվŠa§§Ò¹e¾ ièÁ¢ é¹ËÃoŴŧถาระบบคายความรอน (Exothermic) ระบบจะมพลงงานลดลง
ถาระบบดดความรอน (Endothermic) ระบบจะมพลงงานเพมขน
æµ�¡ÒÃe»ÅÕè¹æ»Å§eo ç¹·ÒÅ»� ¡çÂa§äÁ�ÊÒÁÒö¹íÒÁÒº �§ºo¡Ç�Ò » i¡ iÃiÂÒa§¡Å�ÒǨae¡ i´¢é¹ä �ËÃoäÁ� e¾ÃÒa¡ÒÃe»ÅÕè¹æ»Å§Ë¹è§æ äÁ�ä �e¡ÕèÂÇ¢ �o§
¡ aº¾Åa§§Ò¹·Õèe¢�Ò-oo¡¨Ò¡Ãaººe¾Õ§oÂ�Ò§e ÕÂÇ Â a§¢ é¹oÂÙ�¡ aº¡ÒÃe»ÅÕè¹æ»Å§eo ç¹o·Ã»�o Õ¡ �Ç ¨ §ä �ÁÕ¡Òäi´¤�¹¿�§¡ �ªa¹º�§Ê¶Ò¹aµaÇãËÁ�¢é¹ÁÒeÃÕÂ¡Ç �Ò �¾Åa§§Ò¹oiÊÃa (G)�
Lecture 9 - Thermodynamics III 19
Gibbs Free Energy, G
¾Åa§§Ò¹oiÊÃa (G) ¤ o¾Åa§§Ò¹« è§ÊaÊÁoÂÙ�ã¹Ãaºº ·Õè¾Ã �oÁ¨ae¡ i´» i¡ ià iÂÒËà o¡ÒÃe»ÅÕè¹æ»Å§ (tendency to react)
¹íÒÁÒãª�·íÒ¹ÒÂÇ �Ò » i¡ ià iÂÒËà o¡ÒÃe»ÅÕè¹æ»Å§´ a§¡Å�ÒÇ ¨ae¡ i ¢ é¹eo§ä´ �Ëà oäÁ� (spontaneous)¹íÒÁÒãª�㹡ÒäíҹdzËÒ¤ �ÒÊÁ´uÅe¤ÁÕ (K)
G H TS= −นยาม
Lecture 9 - Thermodynamics III 20
Gibbs Free Energy Change (ΔG)
³ ÊÀÒÇao è¹æ ·ÕèäÁ�ãª�ÊÀÒÇaÁҵðҹ ¡ÒÃe»ÅÕè¹æ»Å§¢o§¾Å a§§Ò¹oiÊÃa (ΔG) ËÒä �¨Ò¡¤ÇÒÁÊ aÁ¾ a¹¸ �
ΔGro = Σ(ΔGf
o)products � Σ(ΔGfo)reactants
¡ÒÃe»ÅÕè¹æ»Å§¢o§¾Åa§§Ò¹oiÊÃa (ΔG) ¢o§ chemical reaction Ëà o transformation ³ ÊÀÒÇaÁҵðҹ ¤íҹdzä �¨Ò¡Êٵõ�o仹Õé
ΔG = ΔH- TΔS
Lecture 9 - Thermodynamics III 21
¤ÇÒÁÊaÁ¾a¹¸ �ÃaËÇ �Ò§¾Å a§§Ò¹oiÊÃa¡aº¤ �Ò¤§·ÕèÊÁ uÅ (K)
c d
a b
[C] [D]Q
[A] [B]′ =
[ ]oG G RT ln Q′Δ = Δ +
oG RTK e−Δ=
Law of Mass Action:
ÊíÒËÃaº» i¡ iÃiÂÒe¤ÁÕ aA + bB = cC + dD
¤ÇÒÁÊaÁ¾a¹ �ÃaËÇ�Ò§ ΔG æÅa Q′ ¤o
³ ÊÀÒÇaÊÁ uÅ ΔG →0, Q′→K
[ ]o
o G0 G RT ln K lnK
RTΔ
= Δ + → → = −LL
Lecture 9 - Thermodynamics III 22
» i¡ iÃiÂÒ¡ÒÃ浡µ aÇ¢o§¹éíÒ ³ 298 K
H2O(l) = H+(aq) + OH-
(aq)
ΔGro = Σ(ΔGf
o)products � Σ(ΔGfo)reactants
·Õèo u³ËÀÙÁi 298 K ¾Åa§§Ò¹oiÊÃa¢o§» i¡ iÃiÂÒ¡ÒÃ浡µ aÇe·�Ò¡ aº
[ ] [ ]2r f ,H Of ,H f ,OH reactantproduct
G G G G
0 ( 157.2) 237.1
79.9 kJ
+ −⎡ ⎤ ⎡ ⎤Δ = Δ + Δ − Δ⎣ ⎦⎣ ⎦= + − − −= +
o o o o
¤�Ò¢o§ ΔG e»�¹ �ºÇ¡� æÊ´§Ç�Ò» i¡ iÃiÂÒe¤ÁÕ¹Õé äÁ�¤Çèae¡ i´¢é¹ä �eo§
Lecture 9 - Thermodynamics III 23
» i¡ iÃiÂÒ¡ÒÃ浡µ aÇ¢o§¹éíÒ ³ 298 K
oo
G RTGK exp e
RT−ΔΔ⎡ ⎤= − =⎢ ⎥⎣ ⎦
H2O(l) = H+(aq) + OH-
(aq)
·Õèo u³ËÀÙÁi 298 K ¤�Ò¤§·ÕèÊÁ uŤíҹdzä �¨Ò¡
332.25
15
14
79.9 10K exp e
8.3143 298
9.9 10
10
−
−
−
×⎡ ⎤= − =⎢ ⎥×⎣ ⎦= ×
≈«è§·Õèe¤ÂeÃÕ¹ÁÒã¹Ãa aºÁa ÂÁ
K = KW= [H+][OH-] = 10-14
Lecture 9 - Thermodynamics III 24
Molar Volume, VMolar Volume ËÁÒ¶§»Ã iÁҵâo§ÊÊÒà (cm3 ËÃo m3) íҹǹ 1 moleª�¹ æ¡�Êã¹ou´Á¤µi íҹǹ 1 oÁÅ (·Õè 298 K, 1.0 atm) ÁÕ¤�Òe·�Ò¡aº 24.5 ÅiµÃ
eª�¹ æÃ�æ¤Å䫵 � íҹǹ 1 oÁÅ (·Õè 298 K, 1.0 atm) ÁÕ»ÃiÁÒµÃe·�Ò¡aº 36.93 cm3
¹íÒÁÒ㪠�·íÒ¹Ò¡ÒÃe¡i »¯ i¡ià iÂÒ/¡ÒÃe»ÅÕè¹æ»Å§·ÕèÁջà iÁÒµÃäÁ �¤§·Õè (« 觨aÁռŵ�o¤ÇÒÁ´ a¹¢o§Ãaºº)
ΔVr = Σ(V)products � Σ(V)reactantso´ÂÁÒ¡æÅ�Ç molar volume ¢o§ �¢o§æ¢ç§� ¨a¤§·Õè äÁ�e»ÅÕè¹æ»Å§¡ aº T, P ÁÒ¡e·�ÒäËÃ�
Lecture 9 - Thermodynamics III 25
» i¡ iÃiÂÒ¢o§ooÅiÇÕ¹¡ aº¤Çoµ« �
Mg2SiO4 + SiO2 → 2MgSiO3
¨§¤íҹdzËһà iÁҵ÷Õèe»ÅÕè¹æ»Å§ÊíÒËÃaº» i¡ iÃiÂÒ¢o§æà �¢�Ò§µ�¹
( )[ ] [ ]
enstatite forsterite qtzproduct reactant
3
V 2 V V V
2(43.79) 31.28 22.69
33.61 cm
⎡ ⎤Δ = − +⎡ ⎤⎣ ⎦ ⎣ ⎦= − +
= + ¤�Ò¢o§ ΔV e» �¹ �ºÇ¡� æÊ´§Ç �Ò» i¡ iÃiÂÒ¹Õé ·íÒãË�»ÃiÁÒµÃe¾ ièÁ¢é¹ a§¹aé¹ ¹�Ò¨ae¡ i´ã¹ÊÀÒÇaæÇ´Å �oÁ·ÕèÁÕ �¤ÇÒÁ a¹µèíÒ�
forsterite qtz enstatite
ΔVr = Σ(V)products � Σ(V)reactants
Lecture 10 - Thermodynamics IV 1
ThermodynamicsThermodynamics o u³Ë¾ÅÈÒʵÃ�
Free Energy Change with varying T & PGeothermometry & GeobarometryEquilibrium ConstantsChemical Potential & Fugacity - Introduction
Lecture 10 - Thermodynamics IV 2
¡ÃaºÇ¹¡Ò÷Õè T & P äÁ�¤§·Õèo´Â»¡µiæÅ �Ç ¡ÃaºÇ¹¡Ò÷ҧ¸Ã³ÕÇ i·ÂÒÊ �ǹãË�¨aÁÕ¡ÒÃe»ÅÕè¹æ»Å§·aé§ou³ËÀÙÁ iæÅa¤ÇÒÁ´ a¹ä»¾Ã �oÁæ ¡a¹ eª �¹ »¯ i¡ià iÂÒ¡Òõ¡¼Å ¡¢o§æÁ¡ÁÒã¹¢³a·Õèe¤Å èo¹µaÇ¢ é¹ÁÒã¡Å �¼iÇoÅ¡
¡ÒäíҹdzËÒ¤ �Ò¢o§ ΔGT,P ¢o§»¯ i¡ià iÂÒ ¨aµ�o§ãª �¤�Ò ΔHof,
ΔSo, ΔCP, æÅa ΔV ³ ÊÀÒÇaÁҵðҹæÅ �Ǥíҹdz (oi¹·ie¡Ãµ) ä»ÊÙ�ou³ËÀÙÁ iæÅa¤ÇÒÁ´ a¹·Õèµ�o§¡Ò÷ÃÒº o´Â㪠�ÊÁ¡ÒÃ
( )atm atm
T Tp
T ,P 298,P p 298,P atm298 298
CG H C dT T S dT V P P
T
Δ⎡ ⎤ ⎡ ⎤Δ = Δ + Δ − Δ + + Δ −⎢ ⎥ ⎢ ⎥
⎣ ⎦ ⎣ ⎦∫ ∫o o
ΔGT,Patm
Lecture 10 - Thermodynamics IV 3
¡ÒùíÒÊÁ¡Òà ΔGT,P ä»»ÃaÂu¡µ �㪠�
ãª�¤íҹdzËÒ �o u³ËÀÙÁiæÅa¤ÇÒÁ´ a¹� ¢o§Ëi¹« 觾ºÇ �ÒÁÕæà �Êo§ª¹ i ¢ é¹ä»oÂÙ� �Ç¡ a¹o �Ò§ÊÁ´uÅ (ΔGT,P = 0)
¡Å�ÒǤo eÃÒ㪠� mineral assemblages e»�¹µ aǺ �§ªÕé T æÅa P ·ÕèÁa¹e¡ i o´Â¡ÒùíÒ¤ÇÒÁÃÙ�·Ò§e·oà �oÁä´¹ÒÁi¡Ê�ÁÒãª� « è§e·¤¹ i¤¹ÕéeÃÒeÃÕÂ¡Ç �Ò Geothermometry (T) æÅa Geobarometry (P)
Lecture 10 - Thermodynamics IV 4
Geothermometry & Geobarometry
( )atm atm
T Tp
T ,P 298,P p 298,P atm298 298
CG H C dT T S dT V P P
T
Δ⎡ ⎤ ⎡ ⎤Δ = Δ + Δ − Δ + + Δ −⎢ ⎥ ⎢ ⎥
⎣ ⎦ ⎣ ⎦∫ ∫
atm atm
atm
298,P 298,P
p ,298,P
H , S ,
C , V
Δ Δ
Δ Δ → คานวณไดจากคาในตาราง
Patm = 1.01325×105 N/m2 (1 atm)
³ ÊÀÒÇaÊÁ uÅ ¡íÒ˹´ãË� ΔGT,P = 0 æÅ �Çæ¡ �ÊÁ¡ÒÃËÒ¤ �Ò¢o§ T ËÃo P oo¡ÁÒ
Lecture 10 - Thermodynamics IV 5
¢�o¤ÇÃÃaÇ a§ã¹¡Òäíҹdz (eÃèo§Ë¹�ÇÂ)
ΔG æÅa ΔH ¤ÇÃe»ÅÕè¹˹ �ÇÂãË�e» �¹ J (æ·¹·Õè¨ae» �¹ kJ)
ΔS æÅa S ÁÕ˹�ÇÂe» �¹ J/K ËÃo J/mol-K
ΔCp æÅa Cp ÁÕ˹�ÇÂe» �¹ J/K ËÃo J/mol-K
P ÁÕ˹�ÇÂe» �¹ N/m2 æÅa T ÁÕ˹�ÇÂe» �¹ Kelvin
1 atm = 1.01325 x 105 N/m2
T (K) = 273.15 + T(oC)R = 8.3143 J/mol-KV ÁÕ˹ �ÇÂe»�¹ m3/mol
Lecture 10 - Thermodynamics IV 6
µ aÇoÂ�Ò§: ¡Òú �Ò¹ #3 ¢�o 6
µ�o§¡Ò÷ÃÒºou³ËÀÙÁ i·Õèæà � kyanite æÅa andalusite oÂÙ� �Ç¡ a¹o �Ò§ÊÁ uÅ ³ ¤ÇÒÁ´ a¹ 1 atm
( )atm atm
T Tp
T ,P 298,P p 298,P atm298 298
CG H C dT T S dT V P P
T
Δ⎡ ⎤ ⎡ ⎤Δ = Δ + Δ − Δ + + Δ −⎢ ⎥ ⎢ ⎥
⎣ ⎦ ⎣ ⎦∫ ∫o o
เทากบศนย(สมดล)
เปดตารางแลวคานวณ
เปดตารางแลวคานวณ
เทากบศนยความดนคงท
æ·¹¤ �ÒµaÇeÅ¢¨Ò¡µÒÃÒ§ (¡Òú �Ò¹ #3) Å§ä» ¨aä �x x
pp
298 298
C0 4285.6 C dT x 9.2 dT 0
T
Δ⎡ ⎤ ⎡ ⎤= − + Δ − − + +⎢ ⎥ ⎢ ⎥⎣ ⎦ ⎣ ⎦
∫ ∫æ¡ �ÊÁ¡Òà ( �ǤoÁÏ)
x = 463.15 K
Lecture 10 - Thermodynamics IV 7
¤ÇÒÁÊaÁ¾a¹¸ �ÃaËÇ �Ò§¾Å a§§Ò¹oiÊÃa¡aº¤ �Ò¤§·ÕèÊÁ uÅ (K)
c d
a b
[C] [D]Q
[A] [B]′ =
[ ]oG G RT ln Q′Δ = Δ +
Law of Mass Action:
ÊíÒËà aº»¯ i¡ ià iÂÒe¤ÁÕ aA + bB = cC + dD
¤ÇÒÁÊaÁ¾a¹¸ �ÃaËÇ �Ò§ ΔG æÅa Q′ ¤ o
³ ÊÀÒÇaÊÁ uÅ ΔG →0, Q′→K
[ ]o
o G0 G RT ln K lnK
RTΔ
= Δ + → → = −LLo
oG RTG
K exp eRT
−ΔΔ⎡ ⎤= − =⎢ ⎥⎣ ⎦
Lecture 10 - Thermodynamics IV 8
oT2 r
T 1 2 1
K H 1 1ln
K R T T
⎡ ⎤ ⎡ ⎤Δ≈ − −⎢ ⎥ ⎢ ⎥
⎣ ⎦ ⎣ ⎦
¤ �Ò K e»ÅÕèÂ¹ä» eÁèoo u³ËÀÙÁ ie»ÅÕè¹
µaÇo �Ò§eª�¹ eÁèo·ÃÒº¤ �Ò¤§·ÕèÊÁ uÅ ³ o u³ËÀÙÁi T1 = 298 K ÊÒÁÒö¤íҹdzËÒ¤ �Ò¤§·ÕèÊÁ uÅ ³ o u³ËÀÙÁio è¹æ ä � o´ÂÊÁÁuµãË�¤ �Ò ΔHr
o äÁ�e»ÅÕè¹æ»Å§ÁÒ¡¹ a¡ã¹ª�ǧo u³ËÀÙÁi·Õèµ�o§¡ÒÃËÒ¤íҹdz
Lecture 10 - Thermodynamics IV 9
[ ]P22 1
P1
K Vln P P
K RT
⎡ ⎤ Δ≈ − −⎢ ⎥
⎣ ⎦
¤ �Ò K e»ÅÕèÂ¹ä» eÁèo¤ÇÒÁ´ a¹e»ÅÕè¹
µaÇo �Ò§eª�¹ eÁèo·ÃÒº¤ �Ò¤§·ÕèÊÁ uÅ ³ ¤ÇÒÁ a¹ P1 = 1.0 atm(1.01325x105 N/m2) ÊÒÁÒö¤íҹdzËÒ¤ �Ò¤§·ÕèÊÁ uÅ ³ ¤ÇÒÁ a¹o è¹æ ä � o´ÂÊÁÁuµiãË�¤ �Ò ΔV äÁ�e»ÅÕè¹æ»Å§ÁÒ¡¹ a¡ 㹪�ǧ¤ÇÒÁ a¹·Õèµ�o§¡Òäíҹdz
Lecture 10 - Thermodynamics IV 10
Chemical Potential
¡Òäíҹdz¤�Ò·Ò§e·oÃ�oÁä´¹ÒÁ i¡Ê �·ÕèeÃÕÂ¹ä» e» �¹¡Òä�Ò·Õèãª�ä �ÊíÒËÃaºÊÒúÃiÊu·¸ iì äÁ�ÁÕÊ iè§e¨ o»¹ eª�¹ ¹éíÒºÃiÊu·¸ iì æÃ�¤Çoµ«� ËÃo forsterite/fayalite («è§e» �¹end members ¢o§æÃ�ooÅ iÇÕ¹)
æµ�ã¹ÊÀÒ¾·Õèe» �¹¨Ãi§·Ò§¸Ã³ÕÇi·ÂÒ¹aé¹ æÃ�µ�Ò§æ Áa¡ÁÕäooo¹e¢�ÒÁÒæ·¹·Õè¡ a¹oÂÙ�eÊÁo ¨¹e¡ i´e» �¹ solid solution «è§¤u³ÊÁºaµi·Ò§e·oÃ�oÁä´¹ÒÁi¡Ê �¢o§ÊÒ÷Õèe» �¹ solid solution ¹Õé äÁ�ÁÕ a§¹aé¹µ�o§ãª�¿�§¡ �ªa¹º�§Ê¶Ò¹a (function of state) µ aÇãËÁ � ÁÒª�ÇÂ㹡ÒûÃaÂu¡µ�ãª�¡ aºæÃ�äÁ�ºÃiÊu·¸ iì
Lecture 10 - Thermodynamics IV 11
Chemical Potential«è§¿�§¡ �ªa¹º�§Ê¶Ò¹a a§¡Å �ÒÇ eÃÕ¡Ç�Ò Chemical Potential (μ)«è§ e» �¹¾ÒÃÒÁ ieµoÃ�·Õèº�§ºo¡¶§ Ãa aº¾Å a§§Ò¹oiÊÃa¢o§æµ�Åa component ·ÕèoÂÙ�ã¹ÊÒõaÇe ÕÂÇ¡ a¹ (phase e ÕÂÇ¡ a¹) ·Õè¾Ã�oÁ¨a·íÒ» i¡ iÃiÂÒ
µaÇoÂ�Ò§eª�¹ æÃ�ooÅiÇÕ¹ ÁÕÊÙµÃe¤ÁÕe»�¹ Fo40Fa60 ËÁÒ¤ÇÒÁÇ �Ò æÃ�ooÅiÇÕ¹ íҹǹ 1 phase ¨aÁÕo§¤ �»Ãa¡oº (component) Êo§oa¹¤o Fo æÅa Fa «è§æµ �ÅaµaÇ¡ç¨aÁÕ chemical potential e»�¹¢o§µ aÇeo§
«è§¶ �ÒooÅiÇÕ¹¹ÕéoÂÙ�ã¹ÊÀÒÇaÊÁ´uÅ ³ ÊÀÒÇa˹ è§æ (T,P) ¤ �Ò chemical potential ¢o§æµ �ÅaµaǨae· �Ò¡ a¹ ËÃo μFo = μFa
(นศ. จะไดเรยนเรองนเพมในระดบสงขนไป)
Lecture 11 - Chemical Equilibrium 1
[[Geo]Geo]ChemicalChemical EquilibriumEquilibrium
Chemical WeatheringSedimentation & Diagenesis
Geochemical Reactions: Solubility & PrecipitationCarbonate EquilibriaRedox Dissolution & Eh-pH DiagramAdsorption, Ion Exchange
Lecture 11 - Chemical Equilibrium 2
[Geo]Chemical Equilibrium
¨Ò¡¹iÂÒÁ¢o§¾Å a§§Ò¹oiÊÃa (ΔG): ·u¡æ Ãaºº¨a¾ÂÒÂÒÁ´íÒe¹i¹ä»ã¹·iÈ·Ò§·Õè¨aÅ´¾Åa§§Ò¹oiÊÃaãË�µèíÒÊu´ ËÃoe»�¹Èٹ � ¹a蹤o �Ãaºº� ¨a¾ÂÒÂÒÁãË �e¢ �ÒÊÙ� �ÊÀÒÇaÊÁ uÅ� (equilibrium) ¹aè¹eo§
« è§ÊÀÒÇaÊÁ uÅ ¨a¢ é¹oÂÙ�¡aº ou³ËÀÙÁ iæÅa¤ÇÒÁ´ a¹ (e·�Ò¹aé¹!!!) ËÒ¡ T&P e»ÅÕèÂ¹ä» Ãaºº¨a¾ÂÒÂÒÁ»Ã aºãË�e¢ �ÒÊÙ�ÊÁ uÅãËÁ �
µÂ. Ëi¹ pegmatite «è§ÁÕæÃ� feldspar oÒ¨e¤ÂoÂÙ�o �Ò§ÊÁ uÅãµ�¼iÇoÅ¡ æµ�eÁèo¶Ù¡Â¡µaÇ¢é¹ÁÒoÂÙ�º¹¼iÇoÅ¡ « è§ T&P e»ÅÕèÂ¹ä» (æÅaÊÊÒÃÃoºæ µaÇÁ a¹¡çe»ÅÕèÂ¹ä» �Ç eª�¹ ÁÕ¹éíÒ ÁÕ CO2) ¨ae¡ i´¡Òü u¾ a§·íÒÅÒ ¡ÅÒÂe» �¹æÃ� i¹
Lecture 11 - Chemical Equilibrium 3
·íÒäÁµ �o§eÃÕ¹ Geochemical Equilibrium
e¾ èoo iºÒ ¡ÃaºÇ¹¡Òüu¾ a§·íÒÅÒ ·Õèe¡i´¢ 鹡aºæà �æÅaËi¹
e¾ èoo iºÒ ¡ÃaºÇ¹¡Òà sedimentation Ëà o¡Òõ¡¼Å ¡/¡Òõ¡µa¡o¹¨Ò¡ÊÒÃÅaÅÒ ¡ÅÒÂe»�¹æà �Ëà oµa¡o¹ª¹i´ãËÁ �e¾ èoo iºÒ ¡ÃaºÇ¹¡Òà diagenesis « è§e»�¹¡ÃaºÇ¹¡Òõ�Ò§æ ·Õèe¡i ¢ 鹡aºµa¡o¹ µaé§æµ�eà ièÁµ¡¨Á ¨¹¡Ãa·a觡ÅÒÂe»�¹Ëi¹ « è§e»�¹¡ÒÃe»ÅÕè¹æ»Å§·a駷ҧ ¡ÒÂÀÒ¾ ªÕÇÀÒ¾ æÅa·Ò§e¤ÁÕ
Lecture 11 - Chemical Equilibrium 4
Mineral Solubility: Sulfate
CaSO4(s) = Ca2+(aq) + SO4
2-(aq)
¡ÒÃÅaÅÒ¢o§æÃ� anhydrite ã¹¹éíÒºÃiÊ u·¸ iì (298K)
[ ] [ ]Δ = − − − −= +=
or product reactantG 553.6 744.5 1321.8
23.7 kJ
23,700 J−⎡ ⎤= = − = ×⎢ ⎥×⎣ ⎦5
sp
23, 700K K exp 7.04 10
8.3143 298.15
Solubility Product
Lecture 11 - Chemical Equilibrium 5
Mineral Solubility: Sulfate
CaSO4(s) = Ca2+(aq) + SO4
2-(aq)
¡ÒÃÅaÅÒ¢o§æÃ� anhydrite ã¹¹éíÒºÃiÊ u·¸ iì (298K) eÁèoÅaÅÒÂæÅ �Ç ¨aµ�o§ÁÕ [Ca2+] = [SO4
2-] o´ÂÊÁÁuµiãË� sulfate ion äÁ�·íÒ» i¡ iÃiÂÒ hydrolysis µ�o¨¹¡ÅÒÂe» �¹ HSO4
- æÅa H2SO4
−
+ − −
−
= ×
= ×
= ×
5sp
2 2 54
2 5
K 7.04 10
[Ca ][SO ] 7.04 10
x 7.04 10+ − − −= = = × = ×2 2 5 3
4[Ca ] [SO ] x 7.04 10 8.4 10 mol/L
¹a蹤o ¤ÇÒÁÊÒÁÒö㹡ÒÃÅaÅÒ¢o§ anhydrite ÁÕ¤�Òe·�Ò¡aº 8.4 mmol/L ËÃo (8.4 mmol/L)*(136 g/mol) = 1,141 mg/L
Lecture 11 - Chemical Equilibrium 6
Çi Õ¡Òäíҹdz·Õè¶Ù¡µ �o§ÁÒ¡¡Ç �Ò
µ�o§ãª�ÊÁ¡ÒÃÊÁ uÅ»Ãa¨ u Charge Balance Equation¼ÅÃÇÁ¢o§»Ãa¨ uºÇ¡ = ¼ÅÃÇÁ¢o§»Ãa¨ uź
¶ �ÒÁÕ common-ion effect (¼Å¢o§äooo¹Ã �ÇÁ) ¨a·íÒãË �¤ÇÒÁÊÒÁÒö㹡ÒÃÅaÅÒÂe»ÅÕèÂ¹ä» æÅa¶ �Ò㪠� CBE ¡Òäíҹdz¨a§�Ò¢ é¹
Lecture 11 - Chemical Equilibrium 7
Charge Balance EquationÊÒÃÅaÅÒÂ BaCl2
¨íҹǹ»Ãa¨ uź =[Cl-] + [OH-] =
¨íҹǹ»Ãa¨ uºÇ¡ 2[Ba2+] + [H+]
¹íÒæÃ� anhydrite ÁÒÅaÅÒÂã¹¹éíÒºÃiÊ u·¸ iì
¨íҹǹ»Ãa¨ uź =2[SO4
2-] + [OH-] =¨íҹǹ»Ãa¨ uºÇ¡ 2[Ca2+] + [H+]
¹íÒæÃ� anhydrite ÁÒÅaÅÒÂã¹ÊÒÃÅaÅÒ 0.01 M CaCl2¨íҹǹ»Ãa¨ uź =
2[SO42-] + [OH-] + [Cl-] =
¨íҹǹ»Ãa¨ uºÇ¡ 2[Ca2+] + [H+]
Lecture 11 - Chemical Equilibrium 8
Carbonate Equilibria: ÊÁ uŤÒà �ºoe¹µ
CO2(g) + H2O(l) = H2CO3(aq)
㹺ÃÃÂÒ¡ÒÈ ÁÕæ¡ �ʤÒà �ºo¹ä´o ço¡ä« � 0.03% (ËÃo 0.0003 atm)
[ ] [ ]Δ = − − − −= +=
or product reactantG 623.1 394.4 237.1
8.4 kJ
8,400 J⎡ ⎤= − =⎢ ⎥×⎣ ⎦
8400K exp 0.03376
8.3143 298.15
Lecture 11 - Chemical Equilibrium 9
Carbonate Equilibria: ÊÁ uŤÒà �ºoe¹µ
CO2(g) + H2O(l) = H2CO3(aq)
ã¹ÊÀÒ¾¸ÃÃÁªÒµi (T=298K, P=1atm) æËÅ �§¹éíÒ¸ÃÃÁªÒµi¨aÁÕ¤ÇÒÁe¢�Á¢�¹¢o§¡Ã´¤ÒÃ�ºo¹i¡ (H2CO3) ¤§·ÕèeÊÁo
−
=
=
≈
2
2 3
CO
2 3
52 3
[H CO ]K
P
[H CO ]0.03376
0.0003[H CO ] 10 mol/L
e¹ èo§¨Ò¡ activity ¢o§¹éíÒ ÁÕ¤ �Òe· �Ò¡ aº 1.0 ¨ §äÁ�»ÃÒ¡¯ã¹ÊÁ¡Òä �Ò¤§·ÕèÊÁ´ uÅ
Lecture 11 - Chemical Equilibrium 10
µ aÇoÂ�Ò§¡ÒÃÅaÅÒ¢o§æà �¤Òà �ºoe¹µ
กรณทไมเกดปฏกรยา Hydrolysis
กรณทเกดปฏกรยา Hydrolysis
» i¡ iÃiÂÒäÎo´ÃäÅ«iÊ ¤o» i¡ iÃiÂÒ·ÕèÊÒÃe¤ÁÕ·íÒãË�¹éíÒe¡ i´¡ÒÃ浡µaÇ
Lecture 11 - Chemical Equilibrium 11
Ion Activity Product (IAP)
ã¹ÊÒÃÅaÅÒÂã´æ ËÒ¡ IAP ¢o§äooo¹ã¹¢o§æ¢ç§ã´æ ÁÕ¤�ÒÊÙ§¡Ç�Ò Ksp æÅ �Ç (ËÃo IAP/Ksp > 1) ¢o§æ¢ç§ a§¡Å �ÒÇ ¨aÁÕ �æ¹Ço¹�Á� Ç�Ò¨aµ¡µa¡o¹ËÃoµ¡¼Å¡
− −= = ×8.35 9spK 10 4.5 10CaCO3(s) = Ca2+
(aq) + CO32-
(aq)
¶ �Òã¹ÊÒÃÅaÅÒÂ˹è§æ ÁÕ [Ca2+] = 4.1x10-4 M, [CO32-] = 7.3x10-4 M
+ − −= ≈ ×2 2 73IAP [Ca ][CO ] 3 10
−
−
×= =
7
8.35sp
IAP 3 1067
K 10a§¹aé¹ æÃ�æ¤Å䫵� ÁÕæ¹Ço¹�ÁÇ�Ò¨aµ¡µa¡o¹
Lecture 11 - Chemical Equilibrium 12
>
=
<
sp
sp
sp
IAP1
K
IAP1
K
IAP1
K
oÂÙ�ã¹ÀÒÇa Supersaturation � µ¡¼Å¡
oÂÙ�ã¹ÀÒÇaÊÁ uÅËà o Equilibrium
oÂÙ�ã¹ÀÒÇa Undersaturation � äÁ�µ¡¼Å¡
¤ÇÒÁËÁÒ¢o§ IAP (ion-activity product)
Lecture 12 - Mineral Solubility 1
GeocGeochemical Equilibriumhemical Equilibrium
Activity & Activity CoefficientEffect of Activity on Mineral DissolutionRedox Dissolution (Example)
Lecture 12 - Mineral Solubility 2
Activity vs. Concentration
㹡Òäíҹdz ÊÁ´ uÅe¤ÁÕ µÒÁËÅa¡æÅ �Ç µ�o§ãª � �activity� äÁ �㪠�¤ÇÒÁe¢ �Á¢ �¹
o´Â activity ¨aÁÕ¤�Ò¹�oÂ¡Ç �Ò¤ÇÒÁe¢ �Á¢ �¹eÊÁoe¹èo§¨Ò¡ã¹ÊÒÃÅaÅÒÂÁÕäooo¹oÂÙ�ÁÒ¡ÁÒÂËÅÒª¹i´ « è§äooo¹¢o§æ¤Åe«ÕÂÁ¨a¶Ù¡Å �oÁÃoº �ÇÂäooo¹Åºoè¹æ ·íÒãË� �äÁ �ÊÒÁÒö·íÒ»¯ i¡ià iÂÒä �eµçÁ·Õè� a§¹aé¹ ¤ÇÒÁe¢ �Á¢ �¹(·Õè¾Ã �oÁ¨a·íÒ»¯ i¡ià iÂÒ)·Õèæ·�¨Ã i§ ¨§¹�oÂŧ
CaSO4(s) = Ca2+(aq) + SO4
2-(aq)
( ) ( )( )
+ −
=2 2
4
4
Ca SO
CaSO
a aK
a
++<2
2Ca
a [Ca ]
Lecture 12 - Mineral Solubility 3
Activity vs. Concentration
a§¹aé¹ �activity� ¨ae»�¹µaǺ �§ºo¡¶§ �effective concentration� « è§ËÁÒ¶§¤ÇÒÁe¢ �Á¢ �¹·ÕèËŧeËÅooÂÙ� « 觾à �oÁ¨a·íÒ»¯ i¡ià iÂÒe¤ÁÕµ�oä» ¤ÇÒÁÊaÁ¾ a¹ �ÃaËÇ�Ò§ �activity� æÅa �concentration� ¤o
o´Â γ ¤o activity coefficient « è§ÁÕ¤�Ò¹�oÂ¡Ç �Ò 1 eÊÁo eª �¹ ÊíÒËà aºäooo¹æ¤Åe«ÕÂÁ
= γi ia [i]
+ ++= γ2 2
2Ca Ca
a [Ca ]
Lecture 12 - Mineral Solubility 4
Activity Coefficient
¤�Ò¢o§ activity coefficient ¤íҹdzä � Ò¡ÊÁ¡ÒÃ
o´Â A e»�¹¤�Ò¤§·Õè« è§¢ é¹oÂÙ�¡aºou³ËÀÙÁ iæÅa¤u³ÊÁº aµiä´oieÅ硵à i¡¢o§ÊÒÃÅaÅÒ æÅa¤�Ò z ¤ o»Ãa u¢o§äooo¹ æÅa¤�Ò I ¤ o¤�Ò¤ÇÒÁæçäooo¹¢o§ÊÒÃÅaÅÒ (Ionic Strength)
⎡ ⎤− γ = −⎢ ⎥+⎣ ⎦
2i
Ilog Az 0.2I
1 I− γ = 2
ilog Az I ËÃoDebye-Huckel
Davies: ãª�ÁÒ¡ã¹·Ò§¸Ã³Õe¤ÁÕ
= ×∑ 2i
1I [i] z
2
Lecture 12 - Mineral Solubility 5
Ionic Strength
¨§¤íҹdzËÒ¤ �Ò ionic strength ¢o§ÊÒÃÅaÅÒ·Õè»Ãa¡oº �Ç 0.1 M BaCl2 æÅa 0.04 M NaNO3
= ×∑ 2i
1I [i] z
2
{ }
{ }
+ − + −= + + − + + + −
= + + − + + + −
=
2 2 2 2 23
2 2 2 2
1I [Ba ]( 2) [Cl ]( 1) [Na ]( 1) [NO ]( 1)
21
[0.1]( 2) [0.2]( 1) [0.04]( 1) [0.04]( 1)20.34
Lecture 12 - Mineral Solubility 6
⎡ ⎤− γ = −⎢ ⎥+⎣ ⎦
2i
Ilog Az 0.2I
1 I
Activity Coefficient
¡íÒ˹´ãË� A = 0.514
a§¹aé¹ activity coefficient ¢o§ Ba2+ ÁÕ¤�Òe·�Ò¡ aº
−
⎡ ⎤− γ = + −⎢ ⎥+⎣ ⎦− γ =
γ = =
2i
i
0.6172i
0.34log (0.514)( 2) 0.2(0.34)
1 0.34log 0.6172
10 0.241
Lecture 12 - Mineral Solubility 7
Activity ÁÕ¼ÅoÂ�Ò§äá aº ¤ÇÒÁÊÒÁÒö㹡ÒÃÅaÅÒÂ
CaSO4(s) = Ca2+(aq) + SO4
2-(aq)
¡ÒÃÅaÅÒ¢o§æÃ� anhydrite ã¹ÊÒÃÅaÅÒ·ÕèÁÕ I = 0.2 (298K)
[ ] [ ]Δ = − − − −= +=
or product reactantG 553.6 744.5 1321.8
23.7 kJ
23,700 J−⎡ ⎤= = − = ×⎢ ⎥×⎣ ⎦5
sp
23, 700K K exp 7.04 10
8.3143 298.15
Solubility Product
Lecture 12 - Mineral Solubility 8
( ) ( )( )
+ − + −
+ −
+ −
− + −
−
γ γ= =
× = γ γ
× =
2 2 2 24 4
4
2 24
2 2Ca SO 4Ca SO
CaSO
5 2 24Ca SO
5
a a [Ca ] [SO ]K
1a
7.04 10 [Ca ][SO ]
7.04 10 (0.28)(0.28)[x][x]
Activity ÁÕ¼ÅoÂ�Ò§äá aº ¤ÇÒÁÊÒÁÒö㹡ÒÃÅaÅÒÂ
+ −= = =2 24[Ca ] [SO ] x 0.029966 M
¹ a蹤o ¤ÇÒÁÊÒÁÒö㹡ÒÃÅaÅÒ¢o§ anhydrite ÁÕ¤ �Òe· �Ò¡ aº 29.966 mmol/L ËÃo (29.966 mmol/L)*(136 g/mol) = 4,075 mg/L
·íÒãË �¤ÇÒÁÊÒÁÒö㹡ÒÃÅaÅÒÂe¾ ièÁÁÒ¡¢ é¹!!!!
Lecture 12 - Mineral Solubility 9
Redox Dissolution
¡ÒÃÅaÅÒ¢o§æà � (Ê�ǹãË�e»�¹æà �« aÅä¿ �) ·ÕèÁÕ¡ÒÃe»ÅÕè¹ʶҹaoo¡« ie´ª a¹ �ÇÂ
+ + = +123 2 2 ( l) 2 3 2 3( aq)2FeCO O 2H O Fe O 2H CO
− + ++ + = + +2 2722 2 2 4FeS O H O 2SO Fe 2H
+ − ++ + = +22 2MnO 4H 2e Mn 2H O
Lecture 12 - Mineral Solubility 10
µ aÇ¡ÒÃÊíÒ¤ a·Õè·íÒãË�e¡ i´¡Òüu¾ a§·íÒÅÒ·ҧe¤ÁÕ
ou³ËÀÙÁi¤ÇÒÁ´ a¹¹éíÒ
¤Òà �ºo¹ä´oo¡ä«´ � (¡Ã´¤Òà �ºo¹ i¡)oo¡« ie¨¹ (e»�¹µ aÇoo¡« iä´Ê�)¡Ã´o è¹æ eª�¹ « aÅ¿�Çà i¡ (ÁÒ¨Ò¡æ¡ �Ê SO2 æÅa SO3)
Lecture 13 - Stability Diagram 1
RedoxRedox, Eh, Eh--pH DiagrampH Diagram
Redox Geochemical ReactionsEh-pH Diagram (Stability Diagram)
Lecture 13 - Stability Diagram 2
¹iÂÒÁ: » i¡ iÃiÂÒoo¡« ie´ª a¹-ÃÕ´ a¡ª a¹
+ + −→ +2 3Fe Fe e
+ − ++ + → +22 2MnO 4H 2e Mn 2H O
Oxidation
Reduction
¤ÒÂoieÅ硵Ão¹æÅ �ÇeÅ¢oo¡«ie´ªa¹e¾ ièÁ¢é¹
ÃaºoieÅ硵Ão¹æÅ �ÇeÅ¢oo¡«ie´ªa¹Å´Å§
Lecture 13 - Stability Diagram 3
Èa¡Â�ä¿¿�Ò¢o§» i¡ iÃiÂÒ (E°)
» i¡ iÃiÂÒÃÕ ço¡«� ¨aÁÕÈ a¡Â �ä¿¿ �Ò¢o§µaÇÁ a¹eo§eÊÁo (¶ �ÒäÁ�ÁÕ¤ÇÒÁµ�Ò§È a¡Â � oieÅ硵Ão¹¡ç¨a¶ �ÒÂoo¹äÁ�ä �) «è§ã¹Ãaºº SI ¡íÒ˹´ãË�¤�Ò E° ¨aµ�o§e» �¹È a¡Â �ä¿¿ �ÒÃÕ a¡ªaè¹eÊÁo
+ − ++ + → +22 2MnO 4H 2e Mn 2H O
+ − ++ →3 2Fe e Fe
Eº = +1.23 V
Eº = +0.77 V
ÃÇÁ¡ a¹¨aä � + + + ++ + → + +2 2 32 2MnO 4H 2Fe Mn 2H O 2Fe
E = (E°)red – (E°)ox = 1.23-0.77 = 0.46 V
Lecture 13 - Stability Diagram 4
¾Åa§§Ò¹oiÊÃa¡ aºÈa¡Â�ä¿¿�Ò¢o§» i¡ iÃiÂÒ
n = ¨íҹǹoÁÅ¢o§oieÅ硵Ão¹·ÕèÁÕ¡Òö �ÒÂe·F = ¤�Ò¤§·Õè¿ÒÃÒe´Â � (96487 ¤ÙÅoÁº �/oÁÅ)E = È a¡Â �ä¿¿ �Ò¢o§» i¡ iÃiÂÒ
+ + + ++ + → + +2 2 32 2MnO 4H 2Fe Mn 2H O 2Fe
E = (E°)red – (E°)ox = 1.23-0.77 = 0.46 V
Δ = −o oG nFE Δ = −G nFE
Δ = −= −= −= −
G nFE
(2)(96487)(0.46)
88, 768.04 J
88.8 kJ
Lecture 13 - Stability Diagram 5
Δ = Δ +
− = − +
= −
o
o
o
G G RT ln Q
nFE nFE RT ln Q
RTE E ln Q
nF
Nernst Equation
+ + + ++ + → + +2 2 32 2MnO 4H 2Fe Mn 2H O 2Fe
+ +
+ +
⎛ ⎞= − ⎜ ⎟
⎝ ⎠
3 2 2o
4 2 2
RT [Fe ] [Mn ]E E ln
nF [H ] [Fe ]
+ +
+ +
⎛ ⎞= − ⎜ ⎟
⎝ ⎠
3 2 2
4 2 2
[Fe ] [Mn ]E 0.46 0.0296 log
[H ] [Fe ]
= −o 2.303RTE E logQ
nF
Lecture 13 - Stability Diagram 6
Stability Diagram of Water (Eh-pH)
pH
Eh
(V
)
4 9
0
1.22
Eh = 1.22 – 0.059pH
Eh =–0.059pH
H2O
H2
H2O
O2
æ¼¹ÀÒ¾æÊ´§eʶÕÂÃÀÒ¾¢o§¹éíÒ㹸ÃÃÁªÒµ i
Ù¡Òäíҹdz �ÇÂÁ o
ÊÀÒ¾oo
¡«iä´Ê�
ÊÀÒ¾
ÃÕiÇ«
�
Eh = E
Lecture 13 - Stability Diagram 7
Eh
(V
)
Stability or Eh-pH Diagram of system Fe(OH)2(s)-Fe(OH)3(s)
Lecture 13 - Stability Diagram 8
Eh-pH Diagram common iron-containing minerals (pyrite, siderite, hematite, magnetite)
eÊ �¹·º ¤o ÁÕ¤ÇÒÁe¢�Á¢�¹¢o§eËÅç¡ [Fe2+] = 10-6 M
Lecture 13 - Stability Diagram 9
æ¼¹ÀÒ¾ Eh-pH eoÒä»ãª �·íÒoaäÃ?µÂ. ¹íÒÁÒ·íÒ¹Òª¹ i´¢o§ �æÃ�� ·Õè¨ae¡ i´¨Ò¡¡ÃaºÇ¹¡Òà diagenesis ã¹ÊÀÒÇaæÇ´Å �oÁ¢o§¡ÒÃÊaÊÁµa¡o¹æººµ�Ò§æ (or vice versa)
Lecture 14 - Weathering 1
Weathering Weathering ¡ÃaºÇ¹¡Òüu¾a§·íÒÅÒ¡ÃaºÇ¹¡Òüu¾a§·íÒÅÒª¹i´¢o§¡Òüu¾ a§·íÒÅÒÂ
Physical, Chemical, and Biological»�¨ a·ÕèÁռŵ�o¡Òüu¾ a§·íÒÅÒÂ
T, P, pH, Eh, Oxygen, CO2, H2O
Êi觷ÕèeËÅo¨Ò¡¡ÃaºÇ¹¡Òüu¾ a§·íÒÅÒ·ҧe¤ÁÕ?What are they and where do they go?
Lecture 14 - Weathering 2
Physical Weathering: ¡Òüu¾ a§·Ò§¡ÒÂÀÒ¾
¡Òüu¾ a§·íÒÅÒ´ �Ç¡Åä¡·Ò§¿ �Êi¡Ê�¢o§¹éíÒ·Õèou³ËÀÙÁiµèíÒ
¡ÒÃæ¢ç§µ aÇæÅa¡ÒÃÅaÅÒÂ-Freeze-thaw weathering¡ÒÃ浡Ãaeºi ¨Ò¡¡Òô٠¹éíÒ-Hydration shattering¼Å¡¹éíÒæ¢ç§oµ¢ é¹-Ice-crystal growth æç´ a¹¹éíÒ-Hydraulic pressure
Lecture 14 - Weathering 3
Physical Weathering: ¡Òüu¾ a§·Ò§¡ÒÂÀÒ¾
Salt weathering ¡ÒÃe¡ i ¼Å¡e¡Åo ¨a a¹ãË�Ëi¹æµ¡Wetting and Drying e»�¡æ æË �§æ ¨a¼ue»�¹¡ÒºInsulation weathering ¼ue»�¹æ¶ºæ ËÃoe»�¹ªaé¹æ ¨a浡e»�¹¡Òº Pressure release ¡ÒÃÅ´æç´ a¹ ¨a浡ã¹ÃÙ»¢o§ Joint Stress corrosion cracking æçe¤ �¹æç¡´ a¹¨¹Ëi¹æµ¡
Lecture 14 - Weathering 4
Biological Weathering: ¡Òüu¾ a§·Ò§ªÕÇÀÒ¾
¡ÒÃe¨Ãieµiºoµ¢o§¾ ª ÊÒþ iÉ (¡Ã´µ�Ò§æ) ·Õè¾ ª»Å �oÂoo¡ÁÒ¡ÒÃËÒ¡ i¹¢o§Ê iè§ÁÕªÕÇiµ¢¹Ò´eÅç¡ eª�¹æº¤·ÕeÃÕ·Õèµ�o§¡ÒÃoo¡« ie¨¹¡Òêo¹äªËÒoÒËÒâo§ÃÒ¡¾ ªæç a¹¨Ò¡¡Ò÷Õèµ�¹äÁ�ãË�¢é¹¡Ã´·Õèe¡ i´¨Ò¡¡ÒÃe¹�Òe» ��o¼u¾ a§¨uÅ i¹·ÃÕ � (溤·ÕeÃÕ eËç´ ÃÒ ÏÅÏ)
Lecture 14 - Weathering 5
Chemical Weathering: ¡Òüu¾ a§·Ò§e¤ÁÕ
¡ÃaºÇ¹¡ÒÃäÎo´ÃäÅ«ÕÊ (Hydrolysis)
¡ÃaºÇ¹¡ÒÃoo¡« ie´ªaè¹-ÃÕ a¡ªaè¹ (Oxidation -Reduction)¡ÃaºÇ¹¡ÒÃà aº¹éíÒæÅaeÊÕ¹éíҼŠ¡ (Hydration-Dehydration)¡ÃaºÇ¹¡ÒÃæÅ¡e»ÅÕè¹o ioo¹ (Ion Exchange)
¡ÃaºÇ¹¡ÒÃÅaÅÒ (Dissolution)
Lecture 14 - Weathering 6
Hydrolysis
e» �¹» i¡ iÃiÂÒ·Õè¹éíÒ桵aÇe» �¹äÎo´Ãe¨¹äooo¹ (H+) æÅaäδÃo¡ä«´ �äooo¹(OH-) æ¡ �Ò¡ a¹e¢�Òä»·íÒ » i¡ iÃiÂÒ
Mg2SiO4 + 4H2O → {2Mg2+ +4OH-} + {4H+ + SiO44-}
→ 2Mg(OH)2 + H4SiO4
Silicic Acid
Lecture 14 - Weathering 7
e» �¹» i¡ iÃiÂÒ·Õè¹éíÒe¢�Òä»·íÒ » i¡ iÃiÂÒÃÇÁ¡ aºæÃ�e iÁã¹Å a¡É³a¹éíҼš ·íÒãË�¼Å¡¢ÂÒµaÇoµ¢é¹ æµ�e¹éoo �o¹Å§æÅa a§ÁÕæç a¹Ãoº·iÈ
2H2O + CaSO4 → CaSO4⋅2H2O¹éíÒ æo¹äÎä´Ãµ�(æ¢ç§)  i»«aÁ(o �o¹ æÅa ÅaÅÒ§�ÒÂ)
¶ �Ò¹éíÒÁÒ¡¡ç¹íÒä»ÊÙ�¡ÒÃÅaÅÒ ËÃo dissolution
Hydration
Lecture 14 - Weathering 8
e» �¹¡ÒÃÅ´ËÃoe¾ ièÁoÕeÅ硵Ão¹ (eÅ¢oo¡«ie´ªa¹) 㹸ҵu·Õè»Ãa¡oºe» �¹æÃ�
MnSiO3 + 1/2 O2 +2H2O = MnO2 + H4SiO4
FeS2 + 7/2 O2 +H2O = Fe2+ + 2H+ + 2SO42-
ºÒ§µaǡ礧·¹æµ�ºÒ§µaÇ¡çÅaÅÒÂä �§�ÒÂËà o¼ueÃçÇ
Oxidation-Reduction
Lecture 14 - Weathering 9
¡Òüu¾ a§·íÒÅÒ·ҧe¤ÁÕ¢o§æÃ� »Ãa¡oº �Ç» i¡ iÃiÂÒÁÒ¡¡Ç�Ò˹觪¹i´eª�¹ acid-base dissoluion æÅ �ǵÒÁ �Ç oxidation-reduction
Combination!!
Lecture 14 - Weathering 10
¤ÇÒÁ¤§·¹¢o§æà �µ �o¡Òüu¾ a§·Ò§e¤ÁÕã¹ÀÒÇa·Õè¼iÇoÅ¡ ¨aÊǹ·Ò§¡ aº¡Òõ¡¼Å¡ã¹ Bowen�s Series
¡Òüu¾a§·Ò§e¤ÁÕ¢o§æÃ�« iÅie¡µ
¤§·¹
µ�o¡Ò
üu¾a§e¾ièÁ¢
é¹
Lecture 14 - Weathering 11
¼Å¨Ò¡¡Òüu¾ a§·íÒÅÒ·ҧ e¤ÁÕ
o§¤ �»Ãa¡oº·Ò§e¤ÁÕe»ÅÕèÂ¹ä» � oÅÙÁ i¹aÁ (Al) Á a¡¨aäÁ �e¤Å èo¹Â �ÒÂä»ä˹ æµ�äooo¹o è¹æ ˹Õoo¡ä»¨Ò¡o¤Ã§Êà �Ò§ (ÁÒ¡º �Ò§ ¹ �oº �Ò§ æÅ �Çæµ�ª¹i´¢o§äooo¹)
o¤Ã§Êà �Ò§¼Å ¡e»ÅÕèÂ¹ä» � æà � íҾǡ« iÅ ie¡µ Ê�ǹãË�¨a¡ÅÒÂe»�¹æà � i¹ (clay minerals) « è§ÁÕo¤Ã§Êà �Ò§e»�¹æ¼�¹æ (layers) Ê�ǹæà � íҾǡ¤Òà �ºoe¹µæÅa« aÅä¿ �¹aé¹ ¨a¡ÅÒÂe»�¹äooo¹ã¹ÊÒÃÅaÅÒÂ
Lecture 14 - Weathering 12
¼Å·Õèe �¹ª a´¢o§¡Òüu¾ a§·íÒÅÒ ¤ o ¨aeËÅoÊ�ǹ·ÕèäÁ�¤ �oÂe¤Å èo¹·Õèeª �¹ aluminum æÅaæà �eËÅ硨ae¾ ièÁ¢ é¹
eÁèoe¡i´ weathering æÅ�Ç ¨aeËÅooaäÃ?
(I) Ëi¹Ê´(II) Ëi¹¼u(III) Ëi¹¼u(IV)Ë i¹¼u
****
Al2O3 ¤�o¹¢�Ò§¤§·Õè äÁ �e»ÅÕè¹æ»Å§ÁÒ¡¹a¡
Lecture 14 - Weathering 13
eÁèoe¡i´ weathering æÅ�Ç ¨aeËÅooaäÃ?
Ëi¹Ê´ Ëi¹¼u ãË � Al2O3
¤§·Õè¡ÒÃe»ÅÕè¹
æ»Å§
ÁÕ¹éíÒe¾ ièÁ¢é¹ã¹o¤Ã§Êà �Ò§ æÃ�eËÅç¡æÅaoÅÙÁi¹ aÁ¨aÁÕÊ a´Ê �ǹe¾ ièÁ¢é¹ e¾ÃÒaäooo¹oè¹æ ˹Õä»e¡oºËÁ´
% ¡ÒÃe»ÅÕè¹æ»Å§
Lecture 14 - Weathering 14
Êi觷ÕèeËÅo¨Ò¡¡Òüu¾ a§¢o§æà �« iÅie¡µ
Êiè§eËÅ�Ò¹Õé ·íÒãË �e¡ i Êi觷Õè»Ãa¡oº¡ a¹¢ é¹ÁÒe»�¹ � i¹ (Soil)�
Lecture 15 - Dispersion 1
Dispersion in Secondary Environment Dispersion in Secondary Environment ¡ÃaºÇ¹¡ÒáÃa¨Òµ aÇ¢o§¸Òµuã¹ÊÀÒÇaæÇ´Å �oÁ·uµ iÂÀÙÁi¡ÃaºÇ¹¡ÒáÃa¨Òµ aÇ¢o§¸Òµuã¹ÊÀÒÇaæÇ´Å �oÁ·uµ iÂÀÙÁi
¡ÒáÃa¨ÒµaÇ¢o§¸Òµu (Dispersion of Elements) ¤ ooaäÃ?ÊÀÒÇaæÇ´Å �oÁ¡ÒáÃa¨ÒµaÇ¢o§¸ÒµuÁÕ¡Õè»ÃaeÀ· æÅaÁÕ¤ÇÒÁÊíÒ¤ a
o �Ò§äú �Ò§?»�¨ a·Õèe»�¹µaǤǺ¤uÁãË�e¡i´¡ÒáÃa¨ÒµaÇ¢o§¸Òµu/æà �ã¹ÊÀÒÇaæÇ´Å �oÁ
溺·uµiÂÀÙÁ i
Lecture 15 - Dispersion 2
Primary Environ. Dispersion - ¡ÒáÃa¨Òµ aÇ¢o§¸Òµuã¹ÊÀÒÇaæÇ´Å�oÁ»°ÁÀÙÁi
ä �æ¡� ã¹Ëi¹oa¤¹Õ
Secondary Environ. Dispersion - ¡ÒáÃa¨Òµ aÇ¢o§¸Òµuã¹ÊÀÒÇaæÇ´Å�oÁ·uµ iÂÀÙÁi
ä �æ¡� ã¹æo�§ÊaÊÁµa¡o¹ (sedmentary basin) Ëà oã¹Ëi¹µa¡o¹
Dispersion ¡ÒáÃa¨Òµ aÇ¢o§¸Òµu
Lecture 15 - Dispersion 3
¡ÒáÃa¨Òµ aÇã¹ÊÀÒÇaæÇ´Å �oÁ»°ÁÀÙÁi - Ëi¹oa¤¹Õ
¸Òµu/æà � ·Õ赡¼Å¡¨Ò¡¡ÒÃeÂç¹µaÇ¢o§æÁ¡ÁÒ ÁÕoaäú �Ò§?o§¤ �»Ãa¡oº¢o§æÁ¡ÁÒ¨aÁÕ¼Åo �Ò§ÁÒ¡µ�o¡ÒÃe¡ i æà � ¶ �ÒæÁ¡ÁÒeà ièÁµ�¹ o§¤ �»Ãa¡oºäÁ�eËÁo¹¡ a¹ ¨aä �Ëi¹·ÕèäÁ�eËÁo¹¡ a¹ËÃoÇ i¸Õ¡ÒÃeÂç¹µaǵ�Ò§¡ a¹ (·aé§æ ·ÕèæÁ¡ÁÒÁÕo§¤ �»Ãa¡oºeËÁo¹¡ a¹) ¡ç·íÒãË �ä �æà �µ�Ò§ª¹ i´¡ a¹Important Factors: Thermodynamics & Composition¨aä �eÃÕ¹µ�oä»ã¹¤Ã è§ËÅa§¢o§e·oÁ
Lecture 15 - Dispersion 4
e˵uã´¨§µ �o§ÁÕ¡ÒáÃa¨Òµ aÇ¢o§¸Òµu/æà �
¼ÅÅa¾ �¨Ò¡¡Òüu¾a§·íÒÅÒ ¨aÁÕºÒ§Ê �ǹ·Õèe¤Å èo¹·Õèä � (mobile) ä �æ¡ � äooo¹ æÅa¤oÅÅo � «è§¨ae¤Å èo¹·Õè仡 aºµ aÇ¡ÅÒ§ eª �¹ ¹éíÒeÁèoÊ �ǹ·Õèe¤Å èo¹·Õèä �eËÅ�Ò¹Õé 仵¡ÊaÊÁã¹æo�§ÊaÊÁµa¡o¹æË �§ãËÁ�·ÕèÁÕÊÀÒÇaäÁ�eËÁo¹e iÁ (Eh, pH, T, P, etc.) ¡çoÒ¨µ¡µa¡o¹eÃÒeÃÕ¡¡ÒÃe¤Å èo¹·Õè¢o§ weathering products ¨Ò¡æËÅ�§e iÁä»ÊÙ�æËÅ�§ãËÁ�Ç �Ò �¡ÒáÃa¨Òµ aÇã¹ÊÀÒÇaæÇ´Å �oÁ·uµ iÂÀÙÁi� ËÃo secondary environment dispersion
Lecture 15 - Dispersion 5
2o Environment Dispersion: ÁÕ溺ä˹º�Ò§?
¡ÒáÃa¨ÒÂã¹ÃÙ»¢o§ÊÒÃÅaÅÒ¡ÒáÃa¨ÒÂã¹ÃÙ»¤oÅÅo �¡Òõ¡¼Å¡¨Ò¡ÊÒÃÅaÅÒ¡ÒÃe¡ i æà �¨Ò¡¡ÒÃà aºËÃoÊÙeÊÕ¹éíÒ¡ÒÃe¡ i æà �¨Ò¡¡ÒÃe»ÅÕè¹Êiè§æÇ´Å�oÁ (Eh, pH, T, P, water content etc.)
Lecture 15 - Dispersion 6
¡ÃaºÇ¹¡Òà Dispersion
Lecture 15 - Dispersion 7
¡ÒÃæ¡ �Ò¢o§ weathering products ã¹ÃÙ»¢o§äooo¹ã¹ÊÒÃÅaÅÒÂ
¡Åu�Á·Õè 1: ÊÒÁÒö¤§oÂÙ�ã¹ÊÒÃÅaÅÒÂä´ �o´ÂäÁ�µ¡µa¡o¹ ¶§æÁ�Ç �ÒÊÒÃÅaÅÒ¨aÁÕ pH ÊÙ§
¡Åu�Á·Õè 2: ¨aµ¡µa¡o¹e»�¹ÊÒûÃa¡oºäδÃo¡ä«´ � · aé§æ ·ÕèÊÒÃÅaÅÒÂoÒ¨ÁÕ pH äÁ�ÊÙ§¹ a¡
¡Åu�Á·Õè 3: ÁÕ»Ãa¨uÊÙ§ «è§¨aÃÇÁµ aÇ¡ aºoo¡«ie¨¹e»�¹ÊÒûÃa¡oºeªi§«�o¹ eª�¹ SO4
2-
Lecture 15 - Dispersion 8
Electrical double layer ¢o§o¹uÀÒ¤¤oÅÅo �·íÒãË�e¡i´¡ÒüÅa¡¡ a¹äÁ�µ¡¨Á§�ÒÂæ
æµ�ã¹ÊÒÃÅaÅÒ·ÕèÁÕ¤ÇÒÁæçäooo¹ÊÙ§æ (high ionic strength) eª�¹ ºÃiedz»Ò¡æÁ �¹éíÒ (¹éíÒ¡Ã�oÂ) ¤ÇÒÁ˹Ңo§ªaé¹ EDL ¨aŴŧ ·íÒãË�o¹uÀÒ¤¤oÅÅo �e¤Å èo¹·ÕèÁÒµi´¡ a¹æÅ �ǵ¡µa¡o¹ e» �¹ i¹´o¹ÊÒÁeËÅÕèÂÁ
Lecture 15 - Dispersion 9
æà �·Õ辺㹠2o Environment
¡Òõ¡¼Å ¡¨Ò¡¤oÅÅo �ä´ �æ¡ � cryptocrystalline quartz (flint, chert, jasper)
¡Òõ¡¼Å ¡¨Ò¡ÊÒÃÅaÅÒÂeª�¹ gypsum, halite, sylvite (ÃÇÁeÃÕÂ¡Ç �Ò evaporites)
¡ÒÃe¡ i´æÃ�¨Ò¡¡ÒÃÃaºËÃoÊÙeÊÕ¹éíÒeª�¹ gypsum ↔ anhydrite
¡ÒÃe¡ i´æÃ�¨Ò¡¡ÒÃe»ÅÕèÂ¹Ê iè§æÇ´Å �oÁ (Eh, pH, T, P, water content etc.) ÊÀÒÇaæÇ´Å �oÁe»ÅÕèÂ¹ä» ·íÒãË� mobility ¢o§æÃ�e»ÅÕèÂ¹ä» �ÇÂ
Lecture 15 - Dispersion 10
ÊÃu»: ¡ÃaºÇ¹¡ÒáÃa¨Òµ aÇ¢o§ weathering products
Lecture 16 - Diagenesis 1
DiagenesisDiagenesis:: ¡ÒÃe»ÅÕè¹æ»Å§·Õèe¡i´¢ 鹡aºµa¡o¹¡ÒÃe»ÅÕè¹æ»Å§·Õèe¡i´¢ 鹡aºµa¡o¹ã¹æo �§ÊaÊÁµa¡o¹¨¹¡Ãa· a觡ÅÒÂe»�¹Ëi¹ã¹æo �§ÊaÊÁµa¡o¹¨¹¡Ãa· a觡ÅÒÂe»�¹Ëi¹
¤ÇÒÁËÁÒ¢o§ diagenesise˵u»�¨ a·Õè·íÒãË�e¡i´ diagenesis ã¹æo �§ÊaÊÁµa¡o¹¡ÃaºÇ¹¡Òà diagenesis ·Õèe¡i ¡aºµa¡o¹
o¹i¹·ÃÕÂ � (inorganic sediments)oi¹·ÃÕÂ � (organic sediments)
æÅa¼ÅÅa¾ �·Õèä �¨Ò¡¡ÃaºÇ¹¡Òà diagenesis
This lecture was partially taken & modified from 205237’s lecture (Dr. Benjavun Ratanasthien).
Lecture 16 - Diagenesis 2
»ÃaÇ aµ i¡ÒÃe¡ i´¢o§Ëi¹µa¡o¹ ÊÒÁÒö·Õè¨aæº�§oo¡e» �¹ 3 Ãa´ aº´ a§¹Õé
1. Sedimentogenesis- ¡ÒÃe¡i µa¡o¹2. Diagenesis - ¡ÒÃe»ÅÕè¹æ»Å§¢o§µa¡o¹
¨¹¡Ãa· a觡ÅÒÂe»�¹Ëi¹µa¡o¹3. Catagenesis - e»�¹ÃaÂaeÇÅÒ¡ÒÃe»ÅÕè¹æ»Å§¢o§e»Åo¡oÅ¡·Õè¨aÁռŵ �oËi¹µa¡o¹ « è§e»�¹eÇÅÒ·ÕèÂÒǹҹÁÒ¡
Lecture 16 - Diagenesis 3
¡ÒÃe»ÅÕè¹æ»Å§ã¹æo �§ÊaÊÁµa¡o¹Diagenesis of Sediments in Sedimentary Basins
Diagenesis ¤ o¡ÒÃe»ÅÕè¹æ»Å§·Ò§e¤ÁÕæÅa¿�Êi¡Ê�¢o§µa¡o¹ ¹aºµaé§æµ�ÇÒÃa·Õèä �µ¡Å§ÁÒÊÙ�æo �§ÊaÊÁµa¡o¹ ¨¹¶§ÃaÂa·Õèe»�¹ pre-erosion oÕ¡ÇÒÃaË¹è§ o´ÂoÂÙ�ÀÒÂäµ�oi·¸i¾Å¢o§
¡ÃaºÇ¹¡Ò÷ҧe¤ÁÕæÅa¿�Ê i¡Ê � (Chemical & Physical Processes)ÊÀÒ¾·Ò§e·¤o·¹i¡ æÅaÀÙÁ i»Ãae·È ·aé§ã¹¡ÒÃÊaÊÁµaÇæÅa¡ÒÃe¡ÅÕè¼iÇ i¹ (Tectonic and morphological conditions in both fields ofaccumulation and denudation)
æÃ�·ÕèÁa¡¨a¾ºã¹¸ÃÃÁªÒµi e» �¹¼Å¢o§·a駡Òõ¡µa¡o¹ æÅa¡ÒÃe»ÅÕè¹æ»Å§ËÅ a§¨Ò¡¡ÒÃÊaÊÁµa¡o¹
Lecture 16 - Diagenesis 4
Diagenesis Ê�ǹãË�¨ae¡ i´ºÃiedzã¡Å �æ ¼iÇoÅ¡
Lecture 16 - Diagenesis 5
SyndiagenesisInitial stage (Acid-Base, Redox, Hydrolysis,
Precipitation, etc.)Early burial stage (dolomitization, hydration,
ion-exchange)Anadiagenesis
Deep Burial StageLithification(Metamorphism)
EpidiagenesisPre-erosion
¡ÃaºÇ¹¡ÒÃe»ÅÕè¹æ»Å§ËÅa§¨Ò¡ÊaÊÁµa¡o¹
Lecture 16 - Diagenesis 6
¡ÃaºÇ¹¡ÒÃe»ÅÕè¹æ»Å§ËÅa§¨Ò¡ÊaÊÁµa¡o¹
Lecture 16 - Diagenesis 7
µ aÇo �Ò§: ¡ÒÃe»ÅÕè¹æ»Å§·Õèe¡ i´¡ aºµa¡o¹
ÁÕ¡ÒÃÅaÅÒÂe¾ ièÁ¢ é¹ (dissolution)ÁÕ¡Òõ¡µa¡o¹ÁÒ¾o¡o¹uÀÒ¤æà �e iÁ (precipitation) eª �¹ cementation ¨Ò¡æ¤Å䫵 �Ëà o¤Çoµ« � Ò¡ÊÒÃÅaÅÒ¹éíÒãµ� i¹e¡i »¯ i¡ià iÂÒ oxidation-reduction ¡aºµa¡o¹µa¡o¹æ¤Å䫵 �ÁÕ¡ÒÃæÅ¡e»ÅÕè¹äooo¹ (Ion-Exchange) ¨¹ºÒ§Ê�ǹ¡ÅÒÂe»�¹o´oÅäÁµ� (dolomite, CaMg(CO3)2)
ÁÕ¡ÒÃú¡Ç¹¨Ò¡Ê iè§ÁÕªÕÇ iµeÅç¡æ (·a駾ªæÅaÊaµÇ �) � burrowËà ooÒ¨¶Ù¡¤ÇÒÁà �o¹-¤ÇÒÁ¡´ a¹ ·íÒãË�o¤Ã§Êà �Ò§¢o§µa¡o¹e»ÅÕè¹
Lecture 16 - Diagenesis 8
Diagenesis ¹ aé¹ ¹o¡¨Ò¡¨a¢é¹oÂÙ�¡ aº T, P æÅ �Ç Å a¡É³a¢o§ÊÀÒÇaæÇ´Å �oÁ (Eh, pH) ¡ç a§Áռŵ�oª¹i´¢o§¡ÃaºÇ¹¡Òõ�Ò§æ ·Õèe¡ i´¡ aºµa¡o¹ã¹æo �§ÊaÊÁµa¡o¹ �ÇÂ