Chemistry 14 Outline Guide

CHEMISTRY 14
The Fundamentals of General Chemistry I
Prof. Noel S. Quiming Department of Physical Sciences and Mathematics

Section TFC || Tuesdays and Fridays: 10:00-11:30AM GAB 105 Table of Contents
Atomic Structure The Development of the Different Atomic Models 1 The Subatomic Particles 2 Quantum Mechanical Model and Quantum Numbers 3 The Periodic Table 6 Periodicity of Properties 7 The Chemical Bond Ionic or Electrovalent Bond 8 The Covalent Bond 9 Properties of Covalent Bonds 14 Theories on Covalent Bonds 14 Changes in Matter Chemical Changes 16 The Mole Concept 16 Empirical and Molecular Formula 18 Stoichiometry19 Nuclear Changes 22 Nuclear vs. Chemical Change 22 Types of Radioactive Decay 23 Types of Nuclear Changes 24 Phases of Matter Intermolecular Forces of Attraction 25 Comparison of the Phases of Matter 26 Phase Changes and Phase Diagrams 26 The Gaseous State 27 Kinetic Molecular Theory 27 The Gas Laws 28 Dalton's Law of Partial Pressures 30 Deviations from Ideal Behavior 30 The Liquid State 30 The Solid State 31 Solutions The Dissolution Process 31 Factors Affecting Solubility 32 Types of Solutions 33 Concentration33 Concentration Units 33 Dilution 34 Colligative Properties 34 Acids and Bases Definitions 35 Types of Acids 36 Titration and Neutralization 36 Chemical Thermodynamics Basic Concepts 37 The First Law of Thermodynamics 38 Heats of Reaction 39 The Second Law of Thermodynamics 41
Entropy41 Gibbs Free Energy (G) 41 Third Law of Thermodynamics 43 Chemical Kinetics Theories on Reaction Rates 44 Factors Affecting Rates of Reactions 44 Chemical Equilibrium Molecular Equilibrium 45 Definitions 45 Factors Affecting Equilibrium 46 Ionic Equilibrium 48
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Chemistry 14: Fundamentals of General Chemistry I
Atomic Structure
The Development of the Different Atomic Models Democritus - proposed that matter is made up of small indivisible atoms - small, hard, infinite and has different shapes - found when something is divided and divided: Ends up with an atom of gold - said that they are always moving and capable of joining - nobody believed him - Aristotle was more believed, where he said that the world is made up of 4 elements John Dalton - Billiard Ball Model Potulates: - matter is made up of tiny indivisible atoms - all atoms are identical - different elements have different atoms - compounds are made by joining atoms - was believed for 100 years until the discovery of subatomic particles J.J. Thompson - Plum Pudding/Raisin Bread Model - he discovered the electron using a cathode ray tube - seen through a neutral gas acting like its negatively charged - this proved that the atom was divisible - he showed that there were negatively charged corpuscles (electrons) in matter - he proposed that there must be another positively charged particle to neutralize the charge - was believed for only 5 years Daltons model was similar to Thompsons model by both believing that the atom is solid. Ernest Rutherford - Nuclear Model - first to propose a nucleus in the atom - performed the gold foil experiment - a stream of alpha rays were aimed perpendicularly at a gold foil - most light passed through the film and some were reflected - proved that the atom is not solid (mostly empty space) - it must have a very small dense area of positive charge - the positive particle proton negated the electron and is 2000 times more massive - no results would give a complete description of the electron - he just assumed they were scattered around the nucleus Limitations of Rutherford - What holds the nucleus? - Why dont the electrons collapse into the nucleus? - Wrong proportion of masses with number of particles. - suggested that there was another particle James Chadwick - he discovered the neutron - showed that the nucleus contained protons and neutrons - nucleons: protons and neutrons Modern Model (Rutherford) vs. Dalton - atoms are divisible - atoms of the same element may not be identical - atoms of an element can be changed into another element by nuclear reactions
Prof. Noel S. Quiming
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The Subatomic Particles Atomic Mass Unit (amu) - mass of 1/12 of a 12C atom Isotopic Notation or
A Z
XZ
where: A is the mass no. and Z is the atomic no.
Atomic No. (Z) = No. of protons = No. of electrons (if neutral) Mass No. (A) = No. of protons + No. of neutrons = No. of electons + No. of neutrons (if neutral) = Z + No. of Neutrons
For Cations (+): No. of protons > No. of electrons For Anions (-): No. of Protons < No. of electrons Charge = algebraic sum of No. of protons and No. of electrons No. of protons
24 12 32 16 63 30
No. of electrons 10 18 28
No. of neutrons 12 16 33
Mg2+ S2Zn2+
12 16 30
Isotopes - atoms of the same element that have the same No. of protons but different No. of neutrons - same Z but different A Examples: 1H 2H 3H; 12C 13C 14C; 235U 238U No. of protons
1
No. of neutrons 0 1 2
Mass Number 1 2 3
H (protium) H (deuterium) H (tritium)
1 1 1
H = proton
+ 13 14
C - used in NMR (Nuclear Magnetic Resonance) C - used in carbon dating t = 5700 years
Atomic Mass - averaged from the masses of isotopes - uses the relative abundance of isotopes Example:
Given:
35 37
Cl : relative abundance = 75.77% Atomic Mass = 34.968 amu Cl : relative abundance = 24.23% Atomic Mass = 36.965 amu
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Average Atomic Mass = (relative abundance 1)(atomic mass 1) + (relative abundance 2)(atomic mass 2) Average Atomic Mass = (0.7577)(34.968) + (0.2423)(36.965) = 35.45 amu
Isobars - atoms of different elements but with the same Mass No. (same A) Isotones - atoms with the same No. of neutrons Niels Bohr - Planetary Model - electrons move in ciruclar orbits (orbitals) - energies are quantized meaning they have definite values - electrons need to absorb energy to jump across orbitals - minimum energy needed = energy difference (E =E)
E = Rh 1 n2 E = E2 E1 = Rh
Rh = Rydberg constant = 2.1 1018 J
= Rh
1 Rh n2 2 1 1 2 2 n2 n1
1 n2 1
- after jumping into the excited state, electrons need to go back to the original orbital releasing light energy.
E= hc h = P lanck s constant c = Speed of Light = 6.63 1034 Js
= 3.0 108 m/s
Example: n=5n=1
E = Rh 1 1 2 n2 n i f 1 1 2 2 1 5 = hc = E (6.63 1034 Js)(3.0 108 m/s) 2.016 1018 J 1 104 nm 1m
= 2.1 1018
= 98.66 nm
= 2.016 1018 J
Application: Flame Tests - wavelengths resulting from energy release result in different colors of light Limitations of Bohr - cannot describe a multi-electron model Quantum Mechanical Model and Quantum Numbers Erwin Schrdinger - Quantum Mechanical Model - electrons move in a 3D space (electron cloud) Orbitals Node - a region in space where there is zero probability of finding an electron s orbitals: s p orbitals: px, py, pz d orbitals: dxy, dxz, dyz, dz^2, dx^2-y^2 Quantum Numbers - sets of numbers that are used to describe electrons
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Symbol Principal Higher n: - higher energy - bigger atom/ electron cloud Angular Momentum or Azimuthal n n = 1 (K shell) = 2 (L shell) = 3 (M shell) and so on... l l = 1 (s shell) = 2 (p shell) = 3 (d shell) = 4 (f sublevel) Magnetic m or ml
Possible Values positive integers (1, 2, 3, ...)
Comments - describes the energy level of an electron - describes the size of the electron cloud - main energy level/ shell - describes the shape of the electron cloud - describes the subshell/sublevel - determines the orientation of space of the electron cloud - describes the orbital - describes the direction of the rotation of the orbital
n=1 n=2 n=3 n=4
l=0 l = 0, 1 l = 0, 1, 2 l = 0, 1, 2, 3
l=1 l=2 l=3
m = -1, 0, +1 m = -2, -1, 0, +1, +2 m = -3, -2, -1, 0, +1, +2, +3
Spin
s or ms
+, -
Paulis Exclusion Principle - no two electrons can have the same set of quantum numbers - same n: same shell - same l: same subshell - same m: same orbital - electrons in the same orbital cannot have the same s - orbitals can only accomodate two electrons No. of orbitals No. of electrons n=1 n=2 n=3 Electron Configuration AUFBAU Building Principle - lower energy levels are filled up first n+l rule - the higher the n+l value, the higher the energy of the subshell - determine the energy level of subshells Example: 4s: n+l = 4+0 = 4 3d: n+l = 3+2 = 5 4p: n+l = 4+1 = 5 - If both n+l values are equal, you describe the one with the higher shell first Examples: H: 1s1 1 He: 1s2 2 4 | Chemistry 14: Fundamentals of General Chemistry I 1 4 9 2 8 32
2 2 2 6
C: 1s 2s 2p
2s: Ground state: 1s:
2p: _ _ __
- orbitals in the same subshell are degenerate with one another (have the same energy) - p orbitals: _ _ __ = _ __ _ = __ _ _ Hund's Rule of maximum Multiplicity - one electron is filled in each orbital first before pairing with an unpaired one Atoms at ground state can undergo excitation into an excited state:
2 2 2 6
C: 1s 2s 2p
2s: Ground state: 1s: 2s: _ Excited state: 1s:

2p: _ _ __
2p: _ _ _
Quantum Numbers for electrons in an orbital: 1s: 2s: 2p: (1, 0, 0, -), (2, 0, 0, -), (2, 1, -1, -), (2, 1, 0, -), (2, 1, +1, -), (1, 0, 0, +) (2, 0, 0, +) (2, 1, -1, +) (2, 1, 0, +) (2, 1, +1, +)
Differentiating Electron: last entering electron - for C: (2, 1, 0, -) paramagnetic - if an atom has an unpaired electron diamagnetic - if there are no unpaired electrons Shortcut: Using noble gases Mn: [Ar]4s23d5 Valence electrons - electrons occupying the outermost energy level C: 5 e- Examples: N: 1s22s22p3 7
2p: _ _ _ 2s: Ground state: 1s: Differentiating Electron: (2, 1, +1, -)

2 2 4 8
Valence Electrons: 5
O: 1s 2s 2p
2p: _ _ 2s: Ground state: 1s: Differentiating Electron: (2, 1, +1, -)

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Mn: 1s22s22p63s23p64s23d5 Ground state: 1s: 2s: 2p: 3s: 3p: 4s: 3d: _ _ _ _ _ Differentiating Electron: (3, 2, +2, -) Valence Electrons: 2 2 2 6 2 6 2 10 6 2 10 3 2 Sb: 1s 2s 2p 3s 3p 4s 3d 4p 5s 4d 5p = [Kr]5s 4d105p3 51 Prof. Noel S. Quiming | 5
Differentiating Electron: (5, 1, +1, -)

73
Ta: 1s22s22p63s23p64s23d104p65s24d105p66s24p145d3 = [Xe]6s24p145d3 Differentiating Electron: (5, 2, 0, -) Valence Electrons: 2 Sr: 1s22s22p63s23p64s23d104p65s2= [Kr]5s2 Differentiating Electron: (5, 0, 0, +)
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Given: Differentiating Elctron: (4, 1, 0, +) Answer: 1s22s22p63s23p64s23d104p5 = [Ar]4s23d104p5 = Bromine Stability - if an atom has no incompletely filled orbitals, then it is stable - completely filled > half filled > random incompletely filled - exceptions in AUFBAU principle because of this Ar: P: 15 S: 16
18
[He]2p63s23p6 3p: (Stable) [He]2p63s23p3 3p: _ _ _ [He]2p63s23p4 3p: _ _
Stability: Ar > P > S Cu: [Ar]4s23d9 [Ar]4s13d10

29
4s: 3d: _ 4s: _ 3d:
(LESS STABLE) (MORE STABLE)
Pseudo-Noble Gases Zn: [Ar]4s23d10 30 Zn2+: [Ar]4s03d10 30

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- completely filled, a relatively stable element - still less stable than a noble gas - psuedo noble gas ion - also stable since all orbitals are filled (most stable ion) (most stable ion) (from 4s23d9)
Fe: [Ar]4s23d6 Fe2+: [Ar]4s03d6 26 26Fe3+: [Ar]4s03d5 Cu: [Ar]4s13d10 Cu+: [Ar]4s03d10 29 29Cu2+: [Ar]4s03d9
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The Periodic Table Anton Laurent Lavosier - tabulated 33 elements in his time - only a simple table with no arrangement Dalton's Chemical Symbols - made symbols for 36 different elements Dobereiner's Law of Triads - groupings with three elements each - based on similar chemical and physical properties Newland's Law of Octaves - arranged the elements into increasing atomic mass horizontally - every 8th element would have same properties as the previous 8th - new rows would start at the 8th element Lothar Meyer - observed similarities in properties in relation with atomic masses Mendeleev and Meyer's Periodic Law - the physical and chemical properties of elements are periodic functions of their atomic weights 6 | Chemistry 14: Fundamentals of General Chemistry I
- discrepancies with elements such as K and Ar - atomic weight is not the bast basis for arranging the elements Moseley's Periodic Law - the physical and chemical properties of elements are periodic functions of their atomic numbers - the modern periodic table is based from this Location of Elements - group no: column - period no: row - electron configuration can be used to tell the locations of elements Old System - Family A: Representative Elements - if the differentiang electron occupies an s or p orbital - group no: # of valence electrons - period no: highest n value - Family B: Transition Elements - if the differentiating electron occupies a d or f orbital - group no: # of electrons in ns + (n-1)d orbitals (roman numerals) - period no: highest n value Examples: Mn: [Ar]4s23d5 25 Cl: [Ne]3s23p5 17 Family B Family A Group No VIIB Period No 4 Group No VIIA Period No 3
IUPAC System - groups numbered 1-18 - group No = no. of electrons in ns (s block) = 10 + no of valence electrons (p block) = no of electrons in ns + (n-1)d (d block) - period no: highest n value Example: P: [He]2p63s23p3 Group 15 15 Period 3
Periodicity of Properties Periodic Properties - mostly obsered at family A, the d and f blocks only differ in the inner electrons Atomic Size/Radius - one-half of the nuclear distance : increasing size - increase in n = higher number of energy levels : decreasing size - same energy level but increase in p+and e - higher electrostatic attraction Ionization Potential/Energy - amount of energy required to remove an electron from a neutral atom to convert it to a positively charged ion - 1st electron: 1st ionization potential, 2nd electron: 2nd ionization potential : decreasing potential - bigger atom = less attraction from nucleus, easier to remove : increasing potential - higher electrostatic atraction Exceptions: - Group 3 < 2 Be: 1s22s2 and 5B: 1s22s22p1 4 Prof. Noel S. Quiming | 7
- since the electron at 2p is farther from the nucleus, it is easier to remove - Group 6 < 5 Be: 1s22s22p3 and 8B: 1s22s22p4 7 - N is already stable and there is an e- - e- repulsion that decreases IP

- noble gases have high IP because of stability Electron Affinity - amount of enegry released when a neutral atom accepts an electron in its outermost shell to becme a negatively charged ion - it is expected to have a negative value : decreasing affinity : increasing affinity - metals have less negative electron affinity while nonmetals have more negative ones Electronegativity - the tendency of an atom to attract electons to itself when it is chemically combined to another atom : decreasing electronegativity : increasing electronegativity - group VIIA/17 (halogens) have high electronagavity values (F = highest) - noble gases do not need to attract electrons because they are stable Effective Nuclear Charge - the positive charge that electrons actually experience - 4Be (1s22s2) has a +4 charge - the electrons in 1s experience a +4 charge - the electrons in 2s do not actually experience a +4 charge because of shielding - the 1s electrons experience a +4 charge while the 2s electrons experience a +2 charge - 5B: 1s22s22p1 - 1s = +5, 2s = +3, 2p = +1 - this is the reason why the electron in the outermost level is the easiest to remove - electrons in the same orbital cannot shield each other
The Chemical Bond

- result of the atomic quest for stability - products have the same electron configuration as noble gases - He: 1s2, others: ns2 np6 (stable octet) Ionic or Electrovalent Bond - electron transfer: metal/metalloid + nonmetal - metal(cation): low ionization potential; nonmetal(anion): high electron affinity - due to electrostatic attraction - forms an ionic bond - electronegativity difference > 1.7 ex. Na: 1s22s22p63s1 (attains stability by losing one electron) 11 Na+: 1s22s22p6 (isoelectronic with Ne) Cl: [Ne]3s23p5 Cl-: [Ne]3s23p6 17 2 10 Cd: [Kr]5s 3d Cd2+:[Kr]5s03d10 (pseudo-noble gas ion) 48 p/e ratio - determines the trend of size between elements and their ions - higher p/e = smaller size - lower p/e = bigger size - the atom shrinks because of increased attraction of electrons to protons 8 | Chemistry 14: Fundamentals of General Chemistry I
#p Fe Fe2+ Fe
3+
#e 26 24 23 Fe > Fe2+ > Fe3+
p/e 1 1.08 1.13
26 26 26
#p Na+ Mg
2+
#e 10 10 10
p/e 1.1 1.2 1.3 N3O

2-
#p 7 8 9
#e 10 10 10 N3->O2->F-
p/e 0.7 0.8 0.9
11 12 13
Al3+
F-
Na+ > Mg2+ > Al3+ The Covalent Bond - between nonmetals, neutral particles/molecules - overlapping of orbitals must occur before electron sharing - forming molecular orbitals - head-on overlap: forms a sigma molecular orbital/bond - occurs on s+s, px+px, hybrid orbitals - lateral overlap: sideways, forms a pi molecular orbital/bond - py+py, pz+pz - creates a node at the center of the bond Polarity - nonpolar covalent bond (ex. H2) - forms between similar atoms - equal electron sharing - EN difference 0.4 - polar covalent bond (ex. C-H) - forms between dissimilar atoms - unequal sharing of electrons - EN difference from 0.4 to 1.7 - creates a dipole moment - pointed to the more electronegative atom
Covalency No. - number of bonds that the atom has form with other atoms - may be regardless of normal covalency number Normal Covalency No. - maximum number of covalent bonds that an atom can form - CN = 8 - No. of valence electrons Examples: C: 8-4=4 O: 8-6=2 N: 8-5=3 Coordinate Covalent Bond - a bond between two atoms in which the shared electrons come from one atom Formal Charge = Group No. - (No. of unshared electrons + No. of bonds) Lewis Dot Structure Steps: (ex: NCl3) 1. No. of valence electrons needed N: 1x8 = 8 Cl: 3x8 = 24 Prof. Noel S. Quiming | 9
TOTAL: 32 valence electrons 2. No. of valence electrons available N: 1x5 = 5 Cl: 3x7 = 21 TOTAL: 26 valence electrons 3. No. of shared electrons: 32-26 = 6 electrons 4. No. of bonds: 6/2 = 3 bonds Formal Charges: FCN: 5-3-2 = 0 FCCl: 7-1-6 = 0
Central atom: highest covalency number NH4+ 1. No. of valence electrons needed N: 1x8 = 8 H: 4x2 = 8 TOTAL: 16 valence electrons 2. No. of valence electrons available N: 1x5 = 5 H: 4x1 = 4 TOTAL: 9 valence electrons - 1 electron(from charge) = 8 electrons 3. No. of shared electrons: 16-8 = 8 electrons 4. No. of bonds: 8/2 = 4 bonds Formal Charges: FCN: 5-4-0 = +1 FCH: 1-1-0 = 0
CO2 1. No. of valence electrons needed C: 1x8 = 8 O: 2x8 = 16 TOTAL: 24 valence electrons 2. No. of valence electrons available C: 1x4 = 4 O: 2x6 = 12 TOTAL: 16 valence electrons 3. No. of shared electrons: 24-16 = 8 electrons 4. No. of bonds: 8/2 = 4 bonds Formal Charges: FCC: 4-4-0 = 0 FCO: 6-4-2 = 0
CO321. No. of valence electrons needed C: 1x8 = 8 O: 3x8 = 24 TOTAL: 32 valence electrons 2. No. of valence electrons available C: 1x4 = 4 O: 3x6 = 18 TOTAL: 22 valence electrons + 2 = 24 3. No. of shared electrons: 32-24 = 8 electrons 4. No. of bonds: 8/2 = 4 bonds Formal Charges: FCC: 4-4-0 = 0 FCO1: 6-4-2 = 0 FCO2: 6-6-1 = -1
Contributing Structures based on Formal Charges - structures with small formal charges (+2, -2, or less) are more likely 10 | Chemistry 14: Fundamentals of General Chemistry I
- formal charges of opposite signs are usually adjacent to each other - highly electronegative atoms should have negative rather than positive formal charges - most stable structures have the largest sum of the EN differences for adjacent atoms - ones with fewer formal charges are more stable Resonance Structures - different lewis structures for the same compound - connected by the same framework of sigma bonds FNO2 1. No. of valence electrons needed F: 1x8 = 8 N: 1x8 = 8 O: 1x8 = 8 TOTAL: 24 valence electrons 2. No. of valence electrons available F: 1x7 = 7 N: 1x5 = 5 O: 1x6 = 6 TOTAL: 16 valence electrons 3. No. of shared electrons: 24-16 = 8 electrons 4. No. of bonds: 8/2 = 4 bonds Structure 1: Double bond to O1 FCF: 0 FCN: +1 FCO1: 0 Structure 2: Double bond to O2 FCF: 0 FCN: +1 FCO1: -1 Structure 3: Double bond to F FCF: +1 FCN: +1 FCO1: -1 FCO2: -1 FCO2: 0 FCO2: -1
- the third structure is not contributing because - F, which is the most electronegative has a positive formal charge - adjacent atoms have charges of the same sign SCN1. No. of valence electrons needed S: 1x8 = 8 C: 1x8 = 8 N: 1x8 = 8 TOTAL: 24 valence electrons 2. No. of valence electrons available S: 1x6 = 6 C: 1x4 = 4 N: 1x5 = 5 TOTAL: 15 valence electrons + 1 = 16 electrons 3. No. of shared electrons: 24-16 = 8 electrons 4. No. of bonds: 8/2 = 4 bonds Structure 1: Double bond to both S and N FCs: 6-4-2 = 0 FCc: 4-4-0 = 0 Structure 2: Triple bond to S FCs: 6-2-3 = +1 FCc: 4-4-0 = 0 Structure 3: Triple bond to N FCs: 6-6-1 = -1 FCc: 4-4-0 = 0 FCN: 5-4-2 = -1 FCN: 5-6-1 = -2 FCN: 5-2-3 = 0
- structure 2 is the least contributing among the structures Exceptions to the Octet Rule 1. Molecules with an odd number of electrons ex: NO2 1. No. of valence electrons needed: Prof. Noel S. Quiming
24 valence electrons | 11
2. No. of valence electrons available: 3. No. of shared electrons: 4. No. of bonds:
17 valence electrons 24-17 = 7 electrons 7/2 = 3.5 bonds
- the resulting structure will have a lone electron - compounds with odd numbers of electrons are called free radicals 2. Needs less than an octet to be stable ex: BF3 - following to octet rule there will be the following formal charges FCB: 3-4-0 = -1 FCF1: 7-1-6 = 0 FCF2: 7-1-6 = 0 FCF3: 7-2-4 = +1 - to remove the formal charges, B should only have 3 bonds to it - BF3 then is very reactive and a Lewis acid 3. Expanded octet - only for elements at period 3 and below ex: PCl5 - 5 bonds attached to P ICl4- - 3 bonds and 2 lone pairs attached to I - to expand an octet, remove the formal charge by adding bonds to the central atom SNF3 1. No. of valence electrons needed: 40 valence electrons 2. No. of valence electrons available: 32 valence electrons 3. No. of shared electrons: 40-32 = 8 electrons 4. No. of bonds: 8/2 = 4 bonds FCS: 6-4-0 = +2 FCN: 5-1-6 = -2 - by adding two more S-N bonds, you can remove the formal charges HClO4 1. No. of valence electrons needed: 42 valence electrons 2. No. of valence electrons available: 32 valence electrons 3. No. of shared electrons: 42-32 = 10 electrons 4. No. of bonds: 5/2 = 5 bonds FCCl: 7-4-0 = +3 FCO: 6-1-6 = -1 - by adding a Cl-O bond to each oxygen except the one bonded to H, you remove the formal charges Molecular Geometry (VSEPR Theory) - based on bonding and nonbonding electrons (valence e-) - search for the geometry with the most minimized electron repulsion between atoms - repulsion: lone e- pair-lone e- pair > lone e- pair-bonding > bonding-bonding hybridization - mixing of two ro more nonequivalnt atomic orbitals to for a new set of equivalent degenerate orbitals 1. HgCl2 Hg: [Xe]6s24f145d10 80 GS: 6s: HS: sp: _ _
ES: 6s: _ 6p: _ __ __ (forms 2 covalent bonds)
sp: Cl Cl LINEAR molecular geometry bond angle: 180 2. BF3 B: 1s22s22p1 5 GS: 2s: 2p: _ __ __ ES: 2s: _ 2p: _ _ __ HS: sp2: _ _ _ (forms 3 covalent bonds) sp2: F F F TRIGONAL PLANAR molecular geometry bond angle: 120 3. CH4 C: 1s22s22p2 6 GS: 2s: 2p: _ _ __ ES: 2s: _ 2p: _ _ _ 12 | Chemistry 14: Fundamentals of General Chemistry I
HS: sp3: _ _ _ _
(forms 4 covalent bonds) TETRAHEDRAL molecular geometry bond angle: 109.5
sp3: H H H H
4. PCl5 P: [Ne]3s23p3 15 GS: 3s: 3p: _ _ _ ES: 3s: _ 3p: _ _ _ 3d: _ __ __ __ __ HS: sp3d: _ _ _ _ _ (forms 5 covalent bonds) sp3d: Cl Cl Cl Cl Cl

TRIGONAL BIPYRAMIDAL molecular geometry bond angle: 120 (equatorial) 90 (axial)
5. SF6 S: [Ne]3s23p4 16 GS: 3s: 3p: _ _ ES: 3s: _ 3p: _ _ _ 3d: _ _ __ __ __ HS: sp3d2:_ _ _ _ _ _ (forms 6 covalent bonds) sp3d2: F F FF F F

OCTAHEDRAL molecular geometry bond angle: 90
Geometries with nonbonding electrons 6. NH3 N: 1s22s22p3 7 GS: 2s: 2p: _ _ _ HS: sp3: _ _ _ (forms 3 covalent bonds and 1 lone pair) sp3: H H H 7. H2O O: 1s22s22p4 8 GS: 2s: 2p: _ _ HS: sp3: _ _ sp3: H H

TRIGONAL PYRAMIDAL molecular geometry bond angle: <109.5 ( 107) or TRIPOD
(forms 2 covalent bonds and 2 lone pairs) BENT or V-SHAPED molecular geometry bond angle: <104.5
8. SF4 S: [Ne]3s23p4 16 GS: 3s: 3p: _ _ ES: 3s: 3p: _ _ _ 3d: _ __ __ __ __ HS: sp3d: _ _ _ _ (forms 4 covalent bonds and 1 lone pair) sp3d: F F F F DISTORTED TETRAHEDRON molecular geometry or SEESAW - lone pair will be found on the equatorial plane to minimize electron repulsion 9. ClF3 Cl: [Ne]3s23p5 17 GS: 3s: 3p: _ ES: 3s: 3p: _ _ 3d: _ __ __ __ __ HS: sp3d: _ _ _ (forms 3 covalent bonds and 2 lone pairs)

sp3d: F F F T-SHAPED molecular geometry - lone pairs will be found on the equatorial plane to minimize electron repulsion 10. XeF2 Xe: [Kr]5s24d105p6 54 GS: 5s: 5p: ES: 5s: 5p: _ 5d: _ __ __ __ __ HS: sp3d: _ _ (forms 2 covalent bonds and 3 lone pairs) sp3d: F F LINEAR molecular geometry - lone pairs will be found on the equatorial plane to minimize electron repulsion 11. BrF5 Br: [Ar]4s23d104p5 35 GS: 4s: 4p: _ ES: 4s: 4p: _ _ _ 4d: _ _ __ __ __ Prof. Noel S. Quiming | 13
HS: sp3d2: _ _ _ _ _ (forms 5 covalent bonds and 1 lone pair)
sp3d2: F FF F F SQUARE PYRAMIDAL molecular geometry 12. XeF4 Xe: [Kr]5s24d105p6 54 GS: 5s: 5p: ES: 5s: 4p: _ _ 5d: _ _ __ __ __ HS: sp3d2: _ _ _ _(forms 4 covalent bonds and 2 lone pairs) sp3d2: FF F F # e- pairs 2 3 hybrid. sp sp2 # bonding 2 3 2 4 4 sp3 3 2 5 5 sp3d 4 3 2 6 6 sp d
3 2
SQUARE PLANAR molecular geometry # nonbonding 0 0 1 0 1 2 0 1 2 3 0 1 2 geometry linear trigonal planar bent (v-shaped) tetrahedral trigonal pyramid bent (v-shaped) trigonal bipyr. seesaw t-shaped linear octahedral square pyramid square planar example HgO2, CO2 BF3 NO2ICH4 NH2 H2O PCl5 SF4 ClF3 XeF2 SF6 BrCl5 XeF4
5 4
Properties of Covalent Bonds 1. Bond polarity - nonpolar bond: EN difference 0.4 - polar bond: 0.4 EN difference 1.7 - ionic bond: 1.7 EN difference ex: H-F > H-Cl > H-Br > H-I (decreasing pattern) 2. Bond dissociation energy - energy meeded to destroy a covalent bond bond polarity bond dissociation energy 3. Bond order - number of bonds present between two atoms bond order bond dissociation energy 4. Bond length - internuclear distance size of atom bond length bond polarity bond length 5. Bond angle - becomes smaller due to the presence of lone pairs - deviations from the normal value - comparing different bond angles - difference in central atom size of central bond angle formed - difference in ligand atoms size of ligand bond angle formed Theories on Covalent Bonds in C2H4: All H in s orbitals and all C are sp2 hybridized C: GS: 2s: 2p: _ _ __ ES: 2s: _ 2p: _ _ _ 14 | Chemistry 14: Fundamentals of General Chemistry I
HS:
sp2: _ _ _ 2p: _
C-C bond: 4 C-H bonds: 1 sigma bond: sp2 - sp2 1 sigma bond: sp2 - s 1 pi bond: p-p single bond double bond - sigma bonds - pi bonds 1 sigma bond - sp2 - sp2 1 pi bond - p - p
- only unhybridized p orbitals can form pi bonds in C2H2: All H in s orbitals and all C are sp hybridized C: HS: sp: _ _ 2p: _ _
C-C bond: 2 C-H bonds: 1 sigma bond: sp - sp 1 sigma bond: sp - s 1 pi bond: py - py 1 pi bond: pz - pz For N and O: the atom follows the hybridization of an adjacent carbon atom if one is present - the unhybridized p orbital is almost always used as an orbital for pi bonds - the exceptions are with compounds such as aniline, where there are adjacent C and N molecules in which due to N following the hybridization of C, forms an unhybridized p orbital not used for bonding (used for lone pairs) this N atom has no pi bonds around it and the electrons in its lone pair is able to delocalize delocalization - movement of pi electrons/lone pairs polycentric molecular orbital - is obtained by having pi electrons delocalize around the atom continuously in loops (continuous delocalization) Molecular Orbital Theory - scope only on homonuclear diatomic atoms (H2, O2, etc) - bonding molecular orbital - result of constructive overlap of molecular orbitals - antibonding molecular orbital - result of destructive overlap of molecular orbitals 2 possible results of orbital overlapping - s orbitals: bonding and antibonding (*) MO - p orbitals: bonding, antibonding (*), p bonding, p antibonding (p*) MO Molecular Orbital Energy Diagram 1. No. of MO formed = No. of atomic orbitals combined 2. Bonding MO will have a lower energy than the original atomic orbital while the antibonding MO will have a higher energy than the original atomic orbital 3. The magnitude of decrease of energy for the bonding MO is equal to the magnitude of increase of the antibonding MO Bond Order = (# e- in BMO - # e- in ABMO) - you can also determine if the molecule is paramagnetic or diamagnetic
| 15
O2, F2, Ne2
B2, C2, N2 *: __ p*: __ __ INCREASING ENERGY
*: __ p*: __ __
2p p: __ __ : __ *: __ 2s : __ *: __ 1s : __ 1s 2s
2p
2p : __ p: __ __ *: __ 2s : __ *: __ 1s : __ 1s 2s
2p
Changes in Matter
Chemical Changes The Mole Concept Formula Mass/Weight - refers to the mas of ionic compounds Molecular mass/Weight - refers to covalent compounds - both are computed by the summation of the atomic weights of the component elements
FW of KCl = AW K + AW Cl = 39.098 + 25.45 = 74.55 amu MW of C6 H12 O6 : C : 6 12.01 = 72.06 H : 12 1.01 = 12.12 = 180.18 amu O : 6 16.00 = 96.00
FW of Ca3 (P O4 )2 : Ca : 3 40.01 = 120.03 P : 2 30.97 = 61.94 O : 8 16.00 = 128.00 = 309.97 amu
Mole - amount of substance that contains as many elementary particles as there are atoms in 12 g of 12C - 1 mole = 6.022145x1023 particles = NA (Avogadro's Number) - symbolizes a collection of particles (like dozen, etc.) - of you collect one mole of atoms, its weight is equal to its atomic mass - molar mass: weight of 1 mol of a substance # of particles -> -> Moles -> x Avogadro's Number Molar Mass # of particles <- x <- Moles <- 16 | -> <- Mass in g Mass in g
Examples: Needed: atoms in 4.21 mol of Pt

(4.21 mol P t) 6.02 1023 atoms P t 1 mol P t = 2.53 1024 atoms
Needed: molecules in 0.286 mol CH4 (0.286 mol CH4 ) 6.02 1023 molecules CH4 1 mol CH4 = 1.72 1023 molecules CH4
same number of C atoms, multiply by 4 for number of H atoms Needed: formula units in 0.50 mol KBr (0.50 mol KBr) 6.02 1023 f ormula units KBr 1 mol KBr = 3.01 1023 f ormula units KBr
ionic compounds exist in a crystal lattice while covalent compounds exist as molecules Needed: moles in 6.07g of CH4 M W : C : 12.01 + H : 4.04 = 16.05 g/mol (6.07g CH4 ) 1 mol CH4 16.05g CH4 = 0.38 mol CH4
Needed: moles in 198g of CHCl3 M W : C : 12.01 + H : 1.01 + Cl : 35.45 3 = 119.37 g/mol (198g CHCl3 ) 1 mol CHCl3 119.37g CHCl3 = 1.66 mol CHCl3
Needed: atoms of H in 25.6g of (N H2 )2 CO (25.6g (N H2 )2 CO) 1 mol (N H2 )2 CO 60.06g (N H2 )2 CO 6.02 1023 molecules (N H2 )2 CO 1 mol (N H2 )2 CO 4 atoms H 1 molecule (N H2 )2 CO
= 1.02 1024 atoms H
Needed: grams of 3.14x1019 molecules of HCN (3.14x1019 molecules HCN ) 1 mol HCN 6.02 1023 molecules HCN 27.03g HCN 1 mol HCN = 1.41 103 g HCN
Percent Composition - percent by mass of each element in a compound

mass% = (molar mass)(no. of moles) (mass of compound)
N aN O3 : 22.99 + 14.01 + 3 16.00 = 85.00 g/mol 22.99 100 = 27.05% N a %N a : 85.00 14.01 100 = 16.48% N %N : 85.00 3 16.00 100 = 56.47% O %O : 85.00 H2 SO4 : 2 1.01 + 32.07 + 4 16.00 = 98.09 g/mol 2 1.01 100 = 2.06% H %H : 98.09 32.07 100 = 32.69% S %S : 98.09 4 16.00 100 = 65.25% O %O : 98.09
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C18 H36 O2 : 12 12.01 + 36 1.01 + 2 16.00 = 284.54 g/mol 12 12.01 100 = 75.98% C %C : 284.54 36 1.01 100 = 12.78% H %H : 284.54 2 16.00 100 = 11.25% O %O : 284.54 Needed: g Al in 371g Al2 O3 Al2 O3 : 2 26.98 + 3 16.00 = 101.96 g/mol 2 26.98 100 = 52.92% Al %Al : 101.96 (371g Al2 O3 )(0.5292) = 196.33g Al
Empirical and Molecular Formula Empirical Formula - formula that is determined experimentally - lowest integer form (simplest)
Given: 0.540g S and 0.538g O 1 mol S = 0.017 mol S 0.017 = 1 32.07g S 1 mol O mol O : (0.538g O) = 0.034 mol O 0.017 = 2 16.00g O mol S : (0.540g S ) Empirical F ormula : SO2
Empirical Formula based on % Composition

Given: 40.96%C 4.58%H 54.50%O Basis: 100g 1 mol C = 3.41 mol C 3.41 = 1 3 = 3 12.01g C 1 mol H = 4.53 mol H 3.41 = 1.33 3 = 4 mol H : (4.58g H ) 1.01 H 1 mol O = 3.41 mol O 3.41 = 1 3 = 3 mol O : (54.50g O) 16.00g O mol C : (40.92g C ) Empirical F ormula : C3 H4 O3 Given: 24.75%K 34.77%Mn 40.51%O Basis: 100g 1 mol K = 0.633 mol K 0.633 = 1 39.10g K 1 mol M n = 0.633 mol M n 0.633 = 1 mol M n : (34.77g M n) 59.94 M n 1 mol O mol O : (40.51g O) = 2.53 mol O 0.633 = 4 16.00g O mol K : (24.75g K ) Empirical F ormula : KM nO4
Experimental Determination (Combustion Analysis) - CO2 produced: C content - H2O produced: H content
18 |
Given: f rom 11.5g ethanol, 22.0g CO2 and 13.5g H2 O produced 1 mol CO2 44.02g CO2 1 mol H2 O mol H : (13.5g H2 O) 18.02g H2 O mol C : (22.0g CO2 ) 1 mol C = 0.500 mol C 0.25 = 2 1 mol CO2 2 mol H = 1.498 mol H 0.25 = 6 1 mol H2 O
12.01 g C = 6.005g C 1 mol C 1.01 g H g H : (1.498 mol H ) = 1.513g H 1 mol H g C : (0.500 mol C ) g O : 11.5 6.005 1.513 = 3.998g O mol C : (3.998g O) 1 mol O 16.00 O = 0.25 mol C 0.25 = 1
Empirical F ormula : C2 H6 O
Molecular Formula 1. Determine the molar mass of the empirical formula (EW) 2. Find the ratio of the molar mass of the compound to the molar mass of the empirical formula (factor = MW/EW) 3. Determine the number of units in the empirical formula of the compound Examples 1. Given: EF : CH2 O M M : 60g/mol CH2 O : 12.01 + 2.02 + 16.00 = 30.03g/mol 20 2 f= 30.03 M F : (CH2 O)2 or C2 H4 O2
2. Given: 14.6%C 39.0%O 46.3%F M M : 82g/mol basis : 100g 146gC 390gO 463gF 1mol 12.01gC 1mol 16.00gO 1mol 19.00gF = 1.217molC 1.217 = 1 = 2.438molO 1.217 = 2 = 2.437molF 1.217 = 2
EF : CO2 F2 CO2 F2 : 12.01 + (2 16.00) + (2 19.00) = 82.01g/mol 82 1 f= 82.01 M F : CO2 F2
Stoichiometry - calculations involving balanced chemical reactions Recipe: balanced chemical reaction Example: 2Na + Cl2 2NaCl (2mol Na + 1mol Cl2 2mol NaCl)
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1. Given: 2H2 + O2 2H2 O Moles of reactants needed? 2 molH2 and 1 molO2 Moles of reactants needed to produce 4 moles of H2 O? 4 molH2 and 2 molO2 Moles of hydrogen needed and water produced from 3 moles of oxygen? 3 molO2 3 molO2 2 molH2 = 6 molH2 1 molO2 2 molH2 O = 6 molH2 O 1 molO2
Mole-Mole Conversions 1. Given: 2N a + Cl2 2N aCl 2.6 molCl2

2.6 molCl2 2 molN aCl 1 molCl2 = 5.2 molN aCl
2. Given: 4N H3 + 5O2 4N O + 6H2 O || 25.00 molN H3 molO2 = 25.00 molN H3 molN O = 25.00 molN H3 molH2 O = 25.00 molN H3
5 molO2 = 31.25 molO2 4 molN H3 4 molN O = 25.00 molN O 4 molN H3 6 molH2 O = 37.5 molH2 O 4 molN H3
Mole-Mass Conversions 1. Given: 2N a + Cl2 2N aCl || 5 molN a

gCl2 = 5.00 molN a 1 molCl2 5 molN a
70.90 gCl2 1 molCl2
= 177.25 gCl2
2. Given: CoCl2 + HF CoF2 + 2HCl || 15 molCoF2 gCoCl2 = 15.00 molCoF2 gHF = 15.00 molCoF2
1 molCoCl2 129.84 gCoCl2 = 1947.6 gCoCl2 1 molCoF2 1 molCoCl2 2 molHF 20.01 gHF = 600.3 gHF 1 molCoF2 1 molHF
Mass-Mole Conversions 1. Given: 2C2 H6 + 7O2 4CO2 + 6H2 0 || 10.0 gH2 O

molC2 H6 = 10.0 gH2 O 1 molH2 O 18.02 gH2 O 2 molC2 H6 6 molH2 O = 0.185 molC2 H6
2. Given: CH4 + 2O2 CO2 + 2H2 O || 24.0 gCH4 molO2 = 24.0 gCH4 1 molCH4 16.05 gCH4 2 molO2 1 molCH4 = 2.99 molO2
Mass-Mass Conversions 1. Given: N2 + 3H2 2N H3 || 2.00 gN2

gN H3 = 2.00 gN2 1 molN2 28.02 gN2
2 molN H3 1 molN2
17.04 gN H3 1 molN H3
= 2.43 gN H3
2. Given: 2N a + I2 2N aI || 93.25 gI2 gN aI = 93.25 gI2 1 molI2 253.8 gI2
2 molN aI 1 molI2
149.89 gN aI 1 molN aI
= 110.14 gN aI
20 |
3. Given: 2KClO3 2KCl + 3O2 || 46.0 gKClO3 gO2 = 46.0 gKClO3 1 molKClO3 122.55 gKClO3
3 molO2 2 molKClO3
32.00 gO2 1 molO2
= 18.02 gO2
Excess Reactant - said to be in excess (there is too much) Limiting Reactant - limits how much product we get. Once it runs out, the reaction stops
1. Given: 2Al + 3Cl2 2AlCl3 || 10.0 gAl || 35.00 gCl2 Limiting Reactant: If Al: gAlCl3 = 10.0 gAl If Cl: gAlCl3 1 molAl 26.98 gAl 1 molCl2 = 35.00 gCl2 70.9 gCl2 2 molAlCl3 2 molAl 2 molAlCl3 3 molCl2 133.33 gAlCl3 = 49.42 gAlCl3 1 molAlCl3 133.33 gAlCl3 = 43.38 gAlCl3 1 molAlCl3
The LR is the reactant that produces less product, so in this reaction, Cl2 is the LR and Al is in excess. The reaction produced 43.38 gAlCl3 Excess: (Law of Conservation of Mass) 35.0gAl + 10.0gCl2 = 45.0greactant 43.48gproduct = 1.12gAl 2. Given: 2Al + F e2 O3 Al2 O3 + 2F e|| 124 gAl || 601 gF e2 O3 a. Limiting Reactant: If Al : gAl2 O3 = 124 gAl If F e2 O3 : gAl2 O3 1 molAl 1 molAl2 O3 101.96 gAl2 O3 = 234.30 gAl2 O3 26.98 gAl 2 molAl 1 molAl2 O3 1 molF e2 O3 1 molAl2 O3 101.96 gAl2 O3 = 383.71g = 601 gF e2 O3 159.7 gF e2 O3 1 molF e2 O3 1 molAl2 O3
Al is the LR The reaction produced 234.30 gAl2 O3 b. Excess: gF e2 O3 = 124 gAl 1 molAl 26.98 gAl 1 molF e2 O3 2 molAl 159.7 gF e2 O3 1 molF e2 O3 = 366.99 gF e2 O3
601gF e2 O3 366.99gF e2 O3 = 234.01gF e2 O3
Percent Yield - the amount of product made in a chemical reaction 1. actual yield 2. theoretical yield - experimental yield, what you got in the lab - what the balanced equation tells what the yield should be
% yield = actual yield theoretical yield 100
1. Given: 2Al + 3CuSO4 Al2 (SO4 )3 + 3Cu || 3.92gAl produced 6.78gCu a. actual yield: 6.78gCu b. theoretical yield: gCu = 3.92gAl c. % yield =
1 molAl 3 molCu 62.55 gCu 26.98 gAl 2 molAl 1 molCu 6.78 gCu 100 = 48.95% 13.85 gCu
= 13.85 gCu
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2. Given: T iCl4 + 2M g T i + 2M gCl2 || actual yield: 7.91 106 gT i a. theoretical yield: 3.54 107 gT iCl4 || 1.13 107 gM g
gT i = 3.54 107 gT iCl4 gT i = 1.13 107 gM g b. % yield =
1 molT iCl4 1 molT i 47.87 gT i = 8.93 106 gT i = LR 189.67 gT iCl4 1 molT iCl4 1 molT i 1 molM g 1 molT i 47.87 gT i = 1.113 107 gT i 24.31 gM g 2 molM g 1 molT i 100 = 88.49%
7.91 106 gT i 8.93 106 gT i
3. Given: CaSO4 CaO + SO3 || at 85% yield: 33.0 gCaSO4 136 gCaSO4 produces 80.07 gSO3 If 100 % complete: 33.0 gCaSO4 0.85 = 38.82 gCaSO4 a. actual yield: gCaO = 38.82 gCaSO4 b. gSO3 1 molCaSO4 196.15 gCaSO4 80.07 gSO3 = 38.82 gCaSO4 136 gCaSO4 1 molCaO 1 molCaSO4 = 22.83gSO3 wt. pure 100 wt. unpure
56.01 gCaO 1 molCaO
= 15.98 gCaO
% purity =
4. Given: 2KN O3 2KN O2 + O2 || gO = 1.42gO2 || gKN O3 = 10gKN O3 gKN O3 = 1.42 gO2 % purity = 1 molO2 32.00 gO2 2 molKN O3 1 molO2 101.11 gKN O3 1 molKN O3 = 8.97 gKN O3 8.97 g 100 = 89.7% 10.0 g
5. Given: 2C4 H10 + 13O2 8CO2 + 10H2 O a. 1.0 kgC4 H10 kgO2 = 1000 gC4 H10 1 molC4 H10 58.14 gC4 H10 13 molO2 2 molC4 H10 32.00 gO2 1 molO2 1 kgO2 1000 gO2 = 3.58 kgO2
b. 89% yield Unused O2 : 3.58 kgO2 89% (3.58 kgO2 )(0.11) = 0.39 kgO2 c. 85% pureO2 || 1 kgO2 Unburned C4 H10 : 100% pureO2 : kgC4 H10 = 1000 gO2 85% pureO2 : kgC4 H10 = 850 gO2 1 molO2 32.00 gO2 2 molC4 H10 13 molO2 58.14 gC4 H10 1 molC4 H10 = 237.59 gC4 H10 1 molO2 32.00 gO2 2 molC4 H10 13 molO2 58.14 gC4 H10 1 molC4 H10 = 279.52 gC4 H10
Unburned C4 H10 = 279.52 237.59 = 41.93 gC4 H10
Nuclear Changes Nuclear Chemistry Nuclear vs. Chemical Change
22 |
Nuclear Change involve the nucleus and inner electrons nucleus opens and p+ and n0 rearrange elements transform into other elements needs/releases a high amount of energy rates usually not affected by P, T, catalyst
Chemical Change involve only valence electrons valence electron transfer/sharing rearrangement of atoms and bonds needs/releases a small amount of energy rates usually affected by P, T, catalyst
Radioactivity - discovered by Marie Curie - the spontaneous disintegration (ionizing radiation) of unstable elements into smaller pieces - these elements that can do this are called radionuclides Types of Radioactive Decay 4 4 1. Alpha Decay - Loss of an a-particle (a helium nucleus): 2 He or 2 - 2 n0 and 2 p+
238 92 U 4 234 90 T h +2 He
0 1 e
2. Beta Decay - Loss of a b-particle (a high energy electron): 1 1 0 - 1 n0 and 1 p+ ( 0 n 1 p +1 e )

131 53 I 0 131 54 Xe +1 e
or
0 1
3. e+ emision - Loss of a positron (a particle that has the same mass as but opposite 0 0 charge than an electron): 1 e or 1 1 0 1 - 1 n0 and 1 p+ (1 p 1 +0 n )
11 6 C 0 11 5 B +1 e
4. g emission - Loss of a g-ray (high-energy radiation that almost always accompanies the 0 loss of a nuclear particle): 0 5. e- capture - Addition of an electron to a proton in the nucleus. As a result, a proton is 1 0 1 transformed into a neutron. 1 p +1 e 0 n - 1 n0 and 1 p+
37 18 Ar 37 +0 1 e 17 Cl
Balancing Nuclear Reactions 1. Conserve Mass No. 2. Conserve atomic no./nuclear charge Examples: 1. 212 P o : decay
212 84 P o 60
2. P b
Co : decay
60 0 1 e +28 N i
4 2
He
+208 82
60 27 Co
Neutron-proton ratios - elements with more than one proton have repulsions between the protons in the nucleus - a strong nuclear force helps keep the nucleus from flying apart - Neutrons play a key role stabilizing the nucleus. Prof. Noel S. Quiming | 23
- For (Z 20) stable neutron-to-proton ratio is 1:1. - larger nuclei takes a greater number of neutrons to stabilize the nucleus. Stable Nuclei - belt of stability shows what nuclides would be stable in certain ratios - nuclei above this belt have too many neutrons -> tend to beta decay - Z > 83 are unstable -> tend to alpha decay Trends Magic Numbers Nuclei with 2, 8, 20, 28, 50, or 82 protons or 2, 8, 20, 28, 50, 82, or 126 neutrons
tend to be more stable
Stability (protons-neutrons): even-even > even-odd odd-even > odd-odd Radioactive Series - Radioactive decay usually is not a one-step nuclear transformation. - series of decays until they form a stable nuclide (often a nuclide of lead). Half-Life - time it takes for a substance to become 50% of its original mass - constant and independent of initial composition Mass Defect MD = theoretical mass - actual mass - some of the mass can be converted into energy (E=mc2) called nuclear binding energy (BE) - energy required to break up a nucleus into its component protons and neutrons.
Given: Mn0 = 1.00867 amu || Mp+ = 1.00728 amu || M60 = 59.933819 amu 27 Co
theoretical : (27p+ 1.00728 amup+ ) + (33n0 1.00867 amun0 ) = 60.48267 amu M = 60.48267 amu 59.933819 amu = 0.548851 amu
Types of Nuclear Changes - nucleus undergoes change as a result of bombardment by elementary particles/nuclei Nuclear Fission - a heavy nucleus dicides and form smaller nuclei - followed by high amount of energy Nuclear Chain Reaction - starts with bombardment and splitting of a radioactive parent - the neutron products bombard other possible nuclei - continues until not enough radioactive nuclides are available (the chain reaction will die out) - Critical Mass - minimum amount of fissionable material present for the chain reaction to be sustained - Supercritical Mass - too much mass that creates an uncontrolled accelerated process that may explode Nuclear Fusion - combination of nuclei - can occur only in very high temperatures (like at stars) - not radioactive - possible to perform in a Tokamak apparatus that uses magnetic fields to generate heat Radiation on Matter 24 | Chemistry 14: Fundamentals of General Chemistry I
Does it pass through? alpha particle beta particle gamma ray
Paper X O O
0.5 cm lead X X O
10 cm lead X X X
Phases of Matter
Intermolecular Forces of Attraction - forces of attractions that exist between molecules - determine: - state - melting and boiling points - solubilities van der Waals or London dispersion forces - weakest of the intermolecular forces - due to uneven electron distributions in neighboring molecules - weak attraction of the nuclei in a molecule for electrons in another - attraction of the + side of a nonpolar molecule to the - side of another - size (and electrons), LDF due to higher polarizability - only type of IFA between nonpolar molecules, present in ALL molecules - only temporary, due to temporary dipole moments - induced dipole-induced dipole attraction nonpolar molecules: total = 0 polar molecules: total = >0 CCl4 - nonpolar because there is a cancellation of dipole moments - electrically neutral
Examples: H2, Cl2, CO2, CH4 (only held by LDF) Dipole-Dipole Attractions - molecules with permanent net dipoles (polar molecules) - partial positive charge on one molecule is electrostatically attracted to the partial negative charge of another - stronger than LDF Examples: SCl2 PCl3, CH3Cl Hydrogen-Bond - special dipole-dipole - H atoms are attracted to F, O and N atoms - stronger than dipole-dipole and LDF volume contraction - occurs when you mix 50mL water and 50mL ethanol Ion-Dipole Attraction - attraction between an ion and a polar molecule - accounts for the solubility of most ionic compounds in polar solvents - the larger the charge the stronger the force What type(s) of intermolecular forces exist between each of the following molecules? HBr (polar): dipole-dipole, LDF CH4 (nonpolar): LDF SO2 (polar): dipole-dipole, LDF Summary of IFAs: (strongest to weakest) - ion-dipole - H-bonding Prof. Noel S. Quiming (ion & polar molecule) (N, O, F attached to H) | 25
- dipole-dipole - ion-induced dipole - dipole-induced dipole - london dispersion forces/Van der Waals
(polar molecules) (ion & nonpolar molecule) (polar & nonpolar molecule) (nonpolar molecules)
Indicators of Strength of IFA 1. Molar Heat of Vaporization (Liquid-Gas) - Heat energy required to evaporate one mole of a given substance at a given temperature - IFA, Hvap Examples: CH4 < SO2 < H2O 2. Boiling Point - vapor pressure = atmospheric pressure - IFA, BPt 3. Vapor Pressure - pressure exerted by a gas on a liquid in which it is in equilibrium - volatility, VP, BPt - IFA, VP 4. Molar Heat of Fusion (Solid-Liquid) - heat energy required to melt one mole of a solid - IFA, Hfus 5. Melting Point - temperature at which the liquid and solid phases coexist in equilibrium - IFA, MPt 6. Viscosity - measure of a fluids resistance to flow. - measured in Nsm-2 (SI Units) or poise (P) or centipoise (cP) - IFA, Viscosity 7. Surface Tension - amount of energy required to stretch or increase the surface of a liquid by a unit area - due to the unbalanced force experience by molecules at the surface of a liquid - drops are spherical because the sphere offers the smallest area for a definite volume. 8. Solubility - max amount of solute that will dissolve in a solvent at a given temperature - interaction, solubility Comparison of the Phases of Matter - solid, liquid and gas - interaction: Solid>Liquid>Gas - gases - total disorder and freedom - liquids - "gliding" movement on top of each other (flow) - solids - vibrations - shape and volume: - solids - definite shape and volume - liquids - indefinite shape, definite volume - gases - indefinite shape and volume - only gases are compressible Phase Changes and Phase Diagrams Molar Heat of Vaporization - Heat energy required to evaporate one mole of a given substance at a given temperature - Energy related to evaporation and condensation +Hvap: evaporation (endothermic) Hvap: condensation (exothermic) 26 | Chemistry 14: Fundamentals of General Chemistry I
boiling point normal boiling point
- vapor pressure = atmospheric pressure - boiling point at 1 atm
Molar Heat of Fusion - is the energy that must be absorbed to melt one mole of a substance melting point/freezing point - the temperature at which the solid and liquid phases coexist in equilibrium Molar heat of sublimation - the energy required to sublime 1 mole of a solid - Hsub = Hfus + Hvap
Phase Diagram - a graphical way to summarize the conditions under which equilibrium exist between the different states of matter. It allows us to predict the phase of a substance that is stable at any given temperature and pressure Triple Point: where all three phases are in equilibrium Critical Point: point where critical Temp. and Pressure is achieved Critical Temperature: highest temperature at which a distinct liquid phase can form Critical Pressure: pressure required to bring about liquefaction at critical temperature Supercritical fluid: fluid existing in critical temperatures negative fusion slope of H2O: causes the lower density of ice than water The Gaseous State - gases are either monoatomic (Ne), diatomic (N2) or polyatomic (CH4) 1. have mass 2. compressible 3. fill containers 4. diffusible 5. exert pressure - force on a gas on container walls Kinetic Molecular Theory - attraction (IFA) vs. dispersion (KE) - basis for Gas Laws - predicts IDEAL GAS behavior Postulate 1: Tiny particles in all matter are in constant motion - constant random straight motion; collide against other molecules or container walls - movement is changed by colliding Postulate 2: Colliding is perfectly elastic - kinetic energy of the system is preserved Postulate 3: Molecular motion is greater at higher temperature. Postulate 4: Volume of gas molecules is negligible compared to the total volume of the container (Vgas<<Vcontainer) - empty spaces are in between particles Postulate 5: No attractive or repulsive force occur. - negligible IFA Gas Variables 1. n: amount of moles - amount of gas - 6.02x1023 particles/mol 2. V: volume - assume Vgas Vcontainer - SI unit: L (1L = 1dm3) 3. T: temperature - average kinetic energy Prof. Noel S. Quiming | 27
- in Kelvin: K = C + 273 4. P: pressure - exerted on the wall of the container - atm, mmHg and torr - 1 atm = 760 torr = 760 mmHg Standard Temperature and Pressure ST: 273K (0C) SP: 1 atm - because the gas behavior varies in different T and P ranges The Gas Laws
1 V Boyle's Law - the P vs V graph is logarithmic P
k = T, n
P V = k
P1 V1 = P2 V2
1. Given: V1 = 0.55L || P1 = 1atm || P2 = 0.40atm || V2 =? P1 V1 = P2 V2 V2 = P1 V1 (1 atm)(0.55 L) = = 1.375 L P2 0.40 atm
2. Given: V1 = 946mL || P1 = 726mmHg || V2 = 154mL || P2 =? P1 V1 = P2 V2 P2 = P1 V1 (726 mmHg )(946 mL) = = 4459.71 mmHg V2 154 mL V =k T V2 V1 = T1 T2
V T Charles' Law - the V vs T graph is linear
k = P, n
1. Given: V1 = 452mL || T1 = 295K || T2 = 460K || V2 =? V2 V1 = T1 T2 V1 T2 (452 mL)(460 K ) V2 = = = 704.81 mL T1 295 K 2. Given: V1 = 3.20L || T1 = 398K || V2 = 1.54L || T2 =? V2 V1 = T1 T2 T 1 V2 (398 K )(1.54 L) T2 = = = 191.54 K V1 3.20 L P =k T P2 P1 = T1 T2
P T Gay-Lussac's Law - the P vs T graph is linear
k = V, n
1. Given: P1 = 3.0atm || T1 = 400K || T2 = 500K || P2 =? P2 P1 = T1 T2 P1 T2 (3.0 atm)(500 K ) P2 = = = 3.75 atm T1 400 K
Combined Gas Law
P 2 V2 P1 V 1 = T1 T2
28 |
1. Given: T1 = 281K || P1 = 6.4atm || V1 = 2.1mL || T2 = 298K || P2 = 1atm || V2 =? V2 = P1 V1 T2 (6.4 atm)(2.1 mL)(298 K ) = 14.25 mL = T 1 P2 (281 K )(1 atm)
2. Given: V1 = 4.0L || P1 = 1.2atm || T1 = 339K || V2 = 1.7L || T2 = 315K || P2 =? P2 = P 1 V1 T2 (1.2 atm)(4.0 L)(315 K ) = 2.62 atm = T1 V2 (339 K )(1.7 L)
Ideal Gas Law

P V = nRT Latm R = 0.08206 molK 1. Given: n = 1.82mol || V = 5.43L || T = 342.5K || P =? P =
Latm (1.82 mol)(0.08206 molK )(342.5 K ) nRT = = 9.42 atm V (5.43 L)
2. Given: n = 2.12mol || P = 6.54atm || T = 349K || P =? V =

Latm (2.12 mol)(0.08206 molK )(349 K ) nRT = = 9.28 L P (6.54 atm)
Density Formula Molar Mass Formula PM RT = M= RT P

1. Given: P = 752mmHg || T = 328K || M MN H3 = 17.04g/mol || =?
1 atm (752 mmHg ) 760 mmHg (17.04 PM = = Latm RT (0.08206 molK )(328 K ) g mol )
= 0.63 g/L
2. Given: P = 779mmHg || T = 335K || M MN H3 = 352.03g/mol || =?

1 atm (779 mmHg ) 760 mmHg (352.03 PM = = Latm RT (0.08206 molK )(335 K ) g mol )
= 13.13 g/L
3. Given: P = 288atm || T = 309K || = 7.71g/L || M M =? MM =
g Latm (7.71 L )(0.08206 molK )(309 K ) RT = = 67.88 g/mol P (288 atm) Through trial and error (MM Cl: 35.45g/mol O: 16.00g/mol) the molecular formula is ClO2
4. Given: 33%Si 67%F || P = 1.20atm || T = 308K || V = 0.210L || mass = 2.38g basis: 100g molSi = 33gSi molF = 67gF EF : SiF3
Latm (2.38 g )(0.08206 molK )(308 K ) gRT RT = = = 168.5 g/mol P VP (0.210 L)(1.20 atm) 168.5 2 f actor : 85.04 M F : Si2 F6
1 molSi = 1.17 molSi 1.17 = 1 28.09 gSi 1 molF = 3.53 molF 1.17 = 3 19.00 gF
EW : 28.09 + (3 19) = 85.09 g/mol MM =
| 29
k = P, T V n Avogadro's Law
1mol = 22.4L at STP (molar vol. of ideal gas at STP)
1. Given: 2C2 H2(g) + 5O2(g) 4CO2(g) + 2H2 O(l) || VC2 H2 = 2.64LC2 H2 VO2 = 2.64 LC2 H2 1 molC2 H2 22.4 LC2 H2 5 molO2 2 molC2 H2 22.4 LO2 1 molO2 = 6. 6 L O 2
2. Given: 2C4 H10(g) + 13O2(g) 8CO2(g) +10H2 O(l) || VC4 H10 = 14.9LC4 H10 VO2 = 14.9 LC4 H10 1 molC4 H10 22.4 LC4 H10 13 molO2 2 molC4 H10 22.4 LO2 1 molO2 = 96.85 LO2
3. Given: 2N aN3(s) 2N a(s) + 3N2(g) || gN aN3 = 60gN aN3 || T = 294K || P = 823mmHg Latm (0.08206 molK )(294K ) 1 molN aN3 3 molN2 = 30.74 LN2 VN2 = 160 gN aN3 1 atm 65.02 gN aN3 2 molN aN3 (823mmHg )
760 mmHg
4. Given: C6 H12 O6(s) + 6O2(g) 6CO2(g) + 6H2 O(l) || gC6 H12 O6 = 5.60gC6 H12 O6 || T = 310K || P = 1atm VCO2 = 5.60 gC6 H12 O6 = 4.74 LCO2 1 molC6 H12 O6 180.18 gC6 H12 O6 6 molCO2 1 molC6 H12 O6
Latm (0.08206 molK )(310K ) (1atm)
Dalton's Law of Partial Pressures

PT = PA + PB + PC + ... + Pn Pn = Xn PT Xn =
nn nT
Ideal Behavior - possible in T and P - if n=1, then PV/RT = 1 Deviations from Ideal Behavior - real gases have volume (ideal gases assume no volume) - real gases have IFA - will cause the pressure on the container wall to decrease Van der Waals Equation for Real Gases
P+ an2 V2 an2 V2 (V nb) = nRT
(V nb) : correct V a: correction due to IFA b: correction due to container walls P+ : correct P
The Liquid State Properties of a Liquid - Liquids are almost incompressible, assume the shape but not the volume of container: - Liquids molecules are held closer together than gas molecules, but not so rigidly that the molecules cannot slide past each other. 1. Viscosity - liquids resistance to flow due to IFA which impedes movement - SA viscosity - IFA viscosity 2. Surface Tension - amount of energy required to increase the surface area of a liquid 30 | Chemistry 14: Fundamentals of General Chemistry I
- T viscosity
- measure of the cohesive force that must be overcome - liquid surfaces tend to have the smallest area (spherical) - IFA Surface Tension Example: Hg > water > ethanol 3. Capillarity/ Capillary Action - rising of a liquid through a narrow space against the pull of gravity Cohesive Force binds molecules to each other (IFA) Adhesive Force binds molecules to a surface meniscus - the shape of the liquid surface. - adhesive forces > cohesive forces - the liquid surface is attracted to its container more than the bulk molecules. Therefore, the meniscus is U-shaped Example: water - cohesive forces > adhesive forces - the meniscus is curved downwards Example: mercury The Solid State Types of Solid crystalline - solids with an ordered atomic arrangement polycrystalline - solids with an many ordered atomic arrangements amorphous - solids without an ordered atomic arrangement
Solutions
- homogenous mixtures - solvent: the component with the higher amount (dissolver) - solute: the component with the lower amount (dissolved) - aqueous solution: water is the solvent Examples: air, antifreeze in water, brass (and other alloys), soda, seawater solid-solid are only called homogenous mixtures The Dissolution Process Solvation/Dissolution: the surrounding of solvent molecules to solute molecules In ionic compounds: - involves attraction of ions to positive and negative parts of the solvent. - the solvent surrounds the ions - H changes - IFA (ionic): ion-dipole Prof. Noel S. Quiming | 31
Polar Molecules Example: - CH3CH2OH is soluble in water due to formation of H-bonds - sucrose is also soluble in water due to formation of H-bonds Substances insoluble in water - oil: oil is immiscible in water because they cannot form H-bonds and oil is nonpolar - the water-water H-bonds are more stronger than the attraction of oil and water Energy Changes in Solvation 1. Separation of Solute Particles (endothermic, +H) 2. Separation of Solvent Particles (endothermic, +H) 3. Formation of interaction between solute and solvent (exothermic -H) In a Solution: sol-sol interaction > sol-sol and solv-solv interactions
Heat of Solution: Hsoln = Hsol-sol + Hsolv-solv + H sol-solv Physical manifestation: exothermic: increase in temperature felt endothermic: decrease in temperature felt
Entropy Changes in Solvation 1. Separation of Solute Particles (+S) 2. Separation of Solvent Particles (+S) 3. Formation of interaction between solute and solvent (-S) In Total: +S in solvation Factors Affecting Solubility 1. Nature of Solute/Solvent - dependent on the polarity of solute and solvent - "like dissolves like" ( IFA, solubility) - polar sol, polar solv - nonpolar sol, nonpolar solv - size, LDF, IFA, solubility Example: C6H12 and glucose - cyclohexane is nonpolar, it doesn't dissolve in water - glucose is polar, it dissolves in water - gases are slightly soluble in water solubility, mass 2. Pressure - only affects gases P, solubility Henry's Law: SG = kPG
3. Temperature solid-liquid: T, solubility (endothermic) for salts Cs2(SO4)3 : exothermic T, solubility gas-liquid: T, solubility 4. Surface Area SA, Solubility Dissolution vs. Chemical Reaction - just because a solid disappears doesn't mean it was dissolved - a chemical reaction may have occurred - dissolution is a physical change while chemical reactions are chemical changes - to check: remove the solvent - if there was remaining solid, it was dissolution - if there was nothing remaining, it was a reaction Solubility: the maximum amount of solute that can be dissolved in a solvent at a certain temperature 32 | Chemistry 14: Fundamentals of General Chemistry I
Types of Solutions Degree of Saturation - qualitative description of concentration 1. saturated - holds as much solute as possible at a certain temperature - the dissolved solute is in equilibrium with the undissolved solute 2. unsaturated - less than max amount of solute is held at a given temperature 3. supersaturated - solvent holds more than the normal possible amount Concentration Concentration Units Molarity (M) - temperature dependent Molality (m) Normality (N)
M= molsol Lsoln molsol kgsolv # equivalent weights Lsoln N =M f M= gsol (M Msol )(Lsoln )
m= N=
# equivalent weights = molsol f Factor 1. Acids f = # of replaceable hydronium ion (H+) Examples: HCl (f = 1) H2SO4 (f = 1, 2; diprotic acid) CH3COOH (f = 1) Polyproptic acid - stepwise (one at a time) donation of H+ - If ionization equation is not given: assume max factor
H3 P O4 (triprotic) H 3 P O 4 H + + H2 P O 4 : f = 1 H2 P O4 H + + HP O4 2 : f = 2
2
HP O4
H + + P O4 3 : f = 3
2. Bases f = # of replaceable OHExamples: NaOH (f = 1) Mg(OH)2 (f = 2, 1) Al2(OH)3 (f = 1, 2, 3) NH3 (f = 1; NH4OH) 3. Salts f = total (+) charges or total (-) charges Examples: NaCl (f = 1) MgO (f = 2) Ca3(PO4)2 (f = 2) 4. Oxidizing Agents f = # of e- gained acidic Examples: M nO4 M n2+ : f = 5 basic/neutral M nO4 M nO2 : f = 3 5. Reducing Agents f = # of e- lost 2+ 3+ Fe Fe : f = 1 Examples: Mass % %(w/w) =
gsol 100 gsoln gsol %(w/v ) = 100 mLsoln mLsol %(v/v ) = 100 mLsoln
| 33
Proof Strength Parts per Million (ppm)
proof = 2 % alcohol ppm =
gsol 106 gsoln or mLsoln mgsol = kgsoln or Lsoln gsol 109 Parts per Billion (ppb) ppb = gsoln or mLsoln gsol = kgsoln or Lsoln
p-Scale
p = log [solute] sol =
(used if concentration is very low)

nsolv nsoln Xsol + Xsolv = 1 solv =
Mole Fraction
nsoln
nsol nsoln = nsol + nsolv
Mole % 100 Dilution
C 1 V 1 = C2 V2
Example: Colligative Properties - dependent only on the amount of particles present non-electrolyte electrolyte - does not dissociate in solution - dissociates in solution ex. 1M C6H12O6 ex. 1M NaCl Na+ + Cl-
For nonvolatile, non-electrolyte solutes: 1. Vapor Pressure Lowering - due to solute particles on the surface - also due to IFA that prevents vaporization of solvent
Pf = solv P P = sol P
2. Boiling Point Elevation 3. Freezing Point Depression
tb = mKb Kb (water) = 0.52 C/m

tf = mKf Kf (water) = 1.86 C/m

m = molality
m = molality
4. Osmotic Pressure Osmosis - movement of solvent to a high concentration of solvent to a low concentration of solvent - movement of solvent to a low concentration of solute to a high concentration of solute - passes through a semi-permeable layer that only allows solvent to pass through
= CRT
C = molar concentration Latm R = 0.08206 molK T = absolute temperature(K )

34 |
van't Hoff factor (i) - considers amount of ionization of electrolyte solutes in solution
tb observed tb theoretical (nonelectrolyte) ex. NaCl (i = 2) CaCl (i = 3) tb observed 2 = mkb i=

For Electrolyte Solutes:
P = i(sol P ) tb = i(mKb )
tf = i(mKf ) = i(CRT )
Unless specified, we assume 100% ionization of electrolyte solute (i = # of ions) DebyeHckel theory - Due to the ionic atmosphere surrounding an ion, the expected i value becomes non-ideal Degree of Dissociation (a)
ireal 1 iideal 1
Acids and Bases
Definitions 1. Arrhenius Theory - acid: yields H3O+ / H+ in solution (hydronium ion) - base: yields OH- in solution Acid Example:
HCl H + Cl
+ +
Base
+ N H3 + H2 O N H4 + OH
2. Brnsted-Lowry Theory - acid: proton donor (proton: H+) - base: proton acceptor - includes conjugate acid-base pairs - strong acids/bases produces a weak conjugate and vice versa Example: Pairs: + HCl + H2 O H3 O + Cl HCl/Cl H O/H3O+ acid c.acid base c.base 2
CH3 COOH + H2 O CH3 COO + H3 O+
acid base c.base c.acid + H2 O + N H3 OH + N H4 acid base c.base c.acid
HCl + H2 O H3 O+ + Cl
N aOH N a + OH
Arrhenius bases Brnsted Lowry Bases - metal hydroxides are only Arrhenius bases 3. Lewis Theory - acid: electron pair acceptor - base: electron pair donor - forms a coordinate covalent bond Example: H + + N H3 N H4
acid base
Acidity: The ease of losing the H+ ion Prof. Noel S. Quiming | 35
Types of Acids Binary Acids - consists only of H and another atom - acidity is dependent on electronegativity, bond strength and bond polarity Examples: HF, HCl, HBr, HI, H2S bond polarity, bond strength, acidity Example: Acidity: HF < HCl < HBr < HI (HF is already considered a weak acid)
Oxyacids - consists of an ionizable H attached to an O - oxygen-containing acids Acidity in Difference of central atoms EN of central atom, Acidity size of central atom, Acidity Example: HClO4 is more acidic than HBrO4 Acidity in Difference of the number of Oxygen Atoms O atoms, Acidity Example: Acidity: HClO < HClO2 < HClO3 < HClO4
Examples of Strong Acids: Polyproptic Acids - ionizes through a series of steps Example: 1st ionization : H2 SO4 + H2 O H3 O+ + HSO4 (complete) H2SO4 (diprotic): 2 + H3 O + SO4 (incomplete) 2nd ionization : HSO4 + H2 O
1st ionization : H3 P O4 + H2 O
H3PO4 (triprotic): 2nd ionization : H2 P O4 + H2 O 2 3rd ionization : HP O4 + H2 O H3 O + + H2 P O 4 (incomplete) 2 H3 O+ + HP O4 (incomplete) 3 H3 O + + P O 4 (incomplete)
- degree of ionization decreases after every ionization step Titration and Neutralization - volumetric process to determine the concentration of a sample Acid-Base Titration: analyte: acid titrant: base (solution of known concentration) indicator: changes color at the endpoint - for 1:1 mole ratio, use M1V1 = M2V2 ex. HCl + N aOH N aCl + H2 O - for other ratios, you can use normality or stoichiometry Example: H2 SO4 + 2N aOH N a2 SO4 + 2H2 O analyte: 10.0 mL, H2SO4 titrant: 0.1M, 25.0 mL, NaOH
Ma = 0.1 molb 1 Lb 0.025 Lb 1 1 mola 2 molb 1 0.01 La = 0.125Macid
Chemical Thermodynamics
- measure of energy changes, spontaneity, etc. 36 | Chemistry 14: Fundamentals of General Chemistry I
Basic Concepts System - The part of the universe on which we wish to focus attention, or any part we want to study. Surroundings - Everything outside the system. Types of systems 1. Open Systems - Has a boundary or wall that allows exchange of heat and matter with its surroundings. - Also known as NONCONSERVATIVE system. 2. Closed Systems - Has a boundary or wall that allows the exchange of heat but NOT matter with its surroundings. - The wall or boundary is known as the diathermal wall. 3. Isolated Systems - Has a boundary or wall that does NOT allow the exchange of heat and matter with its surroundings. - The wall or boundary is known as the adiabatic wall. Properties of a System Extensive Properties - They are dependent on the amount of matter, that is, the properties changes as the quantity changes. Examples: mass, moles, volume, etc. Intensive Properties - They are independent on the amount of matter. Examples: density, molecular mass, boiling point, etc.
Intensive Property =

Extensive Property 1 Extensive Property 2
Examples: MM (g/mol), density (mass/vol)
State Functions - The property of a system that depends only on its present state. (dependent on initial/final states) - They do not depend on the path taken or how the system arrived to its present state. (path-independent) Examples: U, H, S, G, A, V, P, T Non-state functions - Path-dependent: The path should be taken into account when evaluating them. - One needs to determine the change involved and not on the initial and final states. Examples: Work and heat (w and q) State functions can be related to one another using an equation of state. Example: ideal gas equation PV = nRT Non-state functions, can be only evaluated if we know the path or type of change. Variables and Sign Conventions in Thermodynamics U = Change in Internal Energy q H = Change in Enthalpy w S = Change in Entropy Prof. Noel S. Quiming
= Heat = Work | 37
= Change in Gibbs free energy
Unit of energy: Joule (J) Other conversions: 1 calorie = 4.184 J By convention, using the BANK system [(+) - deposit and (-) - withdrawal] (+) q = heat is absorbed by the system (-) q (-) w = heat is released by the system = work is done by the system
(+) w = work is done on the system (+) H = the process is endothermic
(-) H = the process is exothermic
The First Law of Thermodynamics - Law of Conservation of Energy - The internal energy (U): the sum of the kinetic and potential energies of the system. - The internal energy of the system can be changed by flow of work, heat or both
U = q + w
A common type of work associated with chemical processes is work done by a gas (through expansion) or done to a gas (compression). For instance, in automobile engines, the heat from combustion of fuels expands the gases in the cylinder to push back the piston. This work translates into the motion of the car. For gases,
w = P V V = change in volume upon expansion or compression.

Expansion: V2 > V1 w = P V = P (V2 V1 ) Compression: V2 < V1 w = P V = P (V2 V1 ) w = (+) = ()()
= ()(+) w = ( )
Example: Calculate the work associated with the expansion of a gas from 46 L to 64 L at a constant pressure of 15 atm.
1. Given: V1 = 46L ; V2 = 64L ; P = 15atm ; w =? w = P V = P (V2 V1 ) = (15)(64 46) = 270Latm
Converting to Joules: = 270Latm molK 0.08206Latm 0.314J molK = 27357.75J = 27.36kJ 1Latm = 101.325J
Note: R = 0.08206
Latm J = 0.314 molK molk
Example: A balloon is being inflated to its full extent by heating the air inside it. In the final stages of this process, the volume of the balloon changes from 4.00 x 106 L to 4.50 x 106 L by the addition of 1.3 x 108 J as heat. Assuming that the gas expands against a constant pressure of 1.0 atm. Calculate the U for the process.
38 |
U = q + w = q P V = q P (V2 V1 ) = 1.3 108 J (5.0 105 Latm) = 1.79995 108 J
2. Given: V1 = 4.00 106 L ; V2 = 4.50 106 L ; P = 1.0atm ; q = 1.3 108 J = 1.3 108 J (1.0atm)(4.50 106 L 4.00 106 L) J 101.325 Latm
Applications of the First Law of Thermodynamics

at constant pressure: H = q
The H is commonly evaluated instead of the internal energy (U). 1. Obtaining H from U
H = U + (P V )
Considering a chemical reaction,
Hrxn = Urxn + (P V ) P V = nRT (P V ) = (nRT ) (P V ) = ngas RT ngas = moles of gaseous products moles of gaseous reactants
Assuming that all gaseous species are ideal gases:
Therefore,
Hrxn = Urxn + ngas RT

Also, for solids and liquids: H U Heats of Reaction Other Methods to Evaluate H 1. Heat of Formation - Heats of formation at standard state (25C and 1 atm), Hf can be found in tables. - The Hf of pure elements at 25C and 1 atm are ZERO. Examples: C(s, graphite), Br2(l), Hg(l), Cl2(g), Al(s) For Gases: Standard state is at 1.00 atm For Solids: Standard state is at 1.00 M * proper state must be indicated
Therefore,
Hrxn = (nHf , products)(nHf , reactants)
Example: Calculate the Hrxn upon the combustion of 1 mole of glucose, C6H12O6. Given: Hf (CO2) = -393.5 kJ/mol Hf (H2O) = -285.6 kJ/mol Hf (glucose) = -1274 kJ/mol
C6 H12 O6 + 6O2 2CO2 + 6H2 O
= (6mol)
285.6kJ mol
+ (6mol)
393.5kJ mol
(1mol)
1274kJ mol
+ (6mol)
0kJ mol
= 2800.6kJ
Example: Methanol (CH3OH) is often used as a fuel in high performance engines in race cars. Using the data above and below, calculate the enthalpy of combustion per gram of Prof. Noel S. Quiming | 39
methanol and compare that with the enthalpy of combustion per gram of octane (C8H18). Given: Hf (methanol) = -239 kJ/mol Hf (octane) = -269 kJ/mol
2CH3 OH + 3O2 2CO2 + 4H2 O
= (4mol)
285.6kJ mol
+ (2mol)
393.5kJ mol
(2mol)
239kJ mol
+ (3mol)
0kJ mol
= 1451.4kJ 2C 8H18 + 25O2 16CO2 + 18H2 O

= (18mol)
285.6kJ mol
+ (16mol)
393.5kJ mol
(2mol)
269kJ mol
+ (25mol)
0kJ mol
= 10898.8kJ
2. Hess Law - Since enthalpy is a state function it follows that in going from a particular set of reactants to a particular set of products, the change in enthalpy is the same whether the reaction takes place in one step or in a series of steps. - Evaluation of H when Hf data is not available - The H of such reactions can be evaluated using several steps but with the net reaction equal to the desired reaction. DESIRED RXN: N2 (g) N2 (g) 2NO (g) NET: N2 (g) + 2O2 (g) + O2 (g) + O2 (g) + 2O2 (g) 2NO2 (g) 2NO (g) 2NO2 (g) 2NO2 (g) H1 = 68 kJ
H2 = 180 kJ H3 = -112 kJ H2 + H3 = 68 kJ
Note: 1. If the reaction is reversed, the sign of H is also reversed. 2. The magnitude of H is directly proportional to the quantities of reactants and products in the reaction. If the coefficients in a balanced reaction are multiplied by an integer, the value of H is multiplied by the same integer. Example: Diborane (B2H6) is a highly reactive boron hydride, which was once considered as a possible rocket fuel for the U.S space program. Calculate H for the synthesis of diborane from its elements. 2B(s) + 3H2(g) B2 H6(g) Using the following data: Reaction H 2B (s) + 3/2O2 (g) B2O3 (s) -1273 kJ B2H6 (g) + 3O2 (g) B2O3 (s) + 3H2O (g) -2035 kJ H2 (g) + 1/2O2 (g) H2O (l) -286 kJ H2O (l) H2O (g) 44 kJ 3. Evaluation of Lattice Enthalpy, Hlattice (Born-Haber Cycle) - the energy needed to separate an ionic lattice into gaseous ions or the energy released when component ions form ionic compounds. Since, this cannot be determined exactly by experiment, but can be envisioned as the formation of an ionic compound occurring in a series of steps. Reaction H Li (s) Li (g) Hsub Li (g) Li+ (g) + e 1st Ionization Energy 1/2F2 (g) F (g) Hdiss 40 | = 161 kJ = 520 kJ = 77 kJ
F (g) + e F- (g) Electron Affinity Li (s) + 1/2F2 (g) LiF (s) Hf What is the lattice enthalpy of LiF? 4. Hf from Bond Enthalpies Example: H2(g) + F2(g) 2HF(g)
= -328 kJ = -617 kJ
Hrxn = (nH, bonds f ormed)(nH, bonds broken)

Therefore, H = BEH H + BEF F 2BEH F Calculate the Hof of HF. Given that BE of H-H is 432 kJ, F-F is 154 kJ and H-F is 565 kJ. The Second Law of Thermodynamics - basis for predicting if a reaction will be spontaneous or non-spontaneous. - spontaneous if a process will cause an increase in entropy of the universe - The entropy of the universe is increasing. Spontaneous Non-spontaneous - occurs without outside intervention - it occurs and liberates energy at the same time - requires energy to carry out
Measure of spontaneity: S or entropy. Entropy - Degree of disorder/randomness in a system - difficult to measure and quantify - not all reactions with S are spontaneous Gibbs Free Energy (G) - expendable energy of the system - better measure because it takes into account H and S At constant pressure:
G = H T S
(The AGAHTAS equation)
Therefore, G < 0: (-) Spontaneous Process at any T G > 0: (+) Non-spontaneous Process at any T G = 0: System at Equilibrium Cases Common in Chemical Reactions H + T any any S + = G +
Cases Common in Physical Changes H + + T low high high low S + + = G + +
| 41
In physical transformations:
S =
qrev Trev
S =
Htransition Ttransition
Example: Melting: Hfusion = qrev
Tmelt = Trev
Where, qr is the heat released or absorbed while T is temperature in Kelvin. Let us see why water freezes spontaneously at -10C while not at 10C. Given: H = 6.03 x 103 J/mol S = (6.03 x 103 J/mol)/273 K Ttransition = 273 K S = 22.1 J/mol K T (C) -10 0 T (K) 263 273 H (J/mol) 6.03 x 103 6.03 x 103 S (J/mol K) 22.1 22.1 TS (J/mol) 5.81 x 103 6.03 x 103 6.25 x 103 G (J/mol) 2.2 x 102 0 -2.2 x102
10 283 6.03 x 103 22.1 Note: Both S and G are STATE FUNCTIONS! Therefore,
S = (nS, products)(nS, reactants) G = (nG, products)(nG, reactants)

Example: Consider the reaction 2SO2 (g) + O2 (g) 2SO3 (g) The reaction was carried out at 25C and 1 atm. Calculate the H, S and G using the following data: Substance Hf (kJ/mol) S (J/mol K) SO2 (g) -297 248 SO3 (g) -396 257 O2 (g) 0 205
Is the process spontaneous or non-spontaneous? Example:

1. Given: Hf = 1440 cal/mol ; Tf = 0 C a) at 5 C S = 1440 cal/mol 273K 1440 cal/mol 273K = 5.27 cal/molK = 5.27 eu
G = H T S Hf = H T Tf
= 1440 cal/mol 268K = 27.64 cal/mol b) at 0 C G = H T S = 1440 cal/mol 273K =0

c) at 5 C G = H T S = 1440 cal/mol 278K
5.27cal molK
5.27cal molK
= 25.06 cal/mol
Using Standard Entropy of Formation (Sf) Example: Given the data below: 6CO2 + 6H2 O C6 H12 O6 + 6O2 H = 2806 kJ/mol 42 | Chemistry 14: Fundamentals of General Chemistry I
S (CO2 ) = 214 J/mol K S (H2O) = 70 J/mol K
S (glucose) = 212 J/mol K S (O2) = 205 J/mol K
Is photosynthesis a spontaneous at 25C?

G = H T S = H T [(nS, products)(nS, reactants)] = H T (1mol) = 2806kJ 298K = 2806kJ 298K 212J + (6mol) molK 262J K 0.262kJ K 205J molK (6mol)
214J molK
+ (6mol)
70J molK
= 2884.08kJ (not spontaneous at 25o C)
Third Law of Thermodynamics - At absolute zero, or 0 K, -273oC, the entropy of a pure crystalline solid is zero.
S0K = 0
*With this, we are able to evaluate the absolute values of entropy. That is, if we start heating a pure crystalline solid, from T = 0 K to T we get:
S = Sf Si S = Sf
S = Sf S0K
(No delta (S) when reported)
Chemical Kinetics
- area concerned with the speed or rates of reaction - how fast or slow a reaction occurs Rate - measured change of concentration of reactants/products per unit time - you can use any reactant/product to state rate Example: A B reactant: rate =
[A] t
(rate of disappearance of A)
product: rate = The Rate of Reaction: A decreases with time B increases with time
[B ] t
(rate of appearance of B)
Also dependent on Stoichiometry Example: 2A B reactant: rate =
1 [A] 2 t
product: rate =
[B ] t
aA + bB cC + dD
Reactant A: rate =
1 [A] a t 1 [B ] Reactant B: rate = b t
Product C: rate =
1 [C ] c t 1 [D] Product D: rate = d t

| 43
Theories on Reaction Rates Collision Theory - rate is proportional to (number of collisions)/(time) [frequency of collision] - frequency, rate - effective collision is needed Effective Collision 1. colliding molecules: energy minimum energy requirement (activation energy (Ea) or energy barrier) activation energy: the minimum amount of energy required to initiate a chemical reaction 2. proper orientation is needed Reaction Profile - plot of the potential energy vs. time of a reaction (progress) Conclusions from Reaction Profiles: - the one with a lower Ea will occur faster Ea: faster Ea: slower - you can determine the energy of the reactants and products - you can determine if the reaction is exothermic/endothermic - if the reaction is reversible, you can compute for the Ea of both directions - you can also determine the number of steps in the reaction - single step: concerted - no. of peaks = no. of steps Proper Orientations - if the molecules are not properly oriented, they will not form the products Transition State Theory - the reactants will form a transition site before forming the products - unstable arrangement of atoms - reactants in a short-lived, high-energy, intermediate state Initial: A + B-B Transition: A--B--B Final: A-B + B
- exact structure cannot be determined - the rate of the reaction is dependent on the energy required to form the transition state energy requirement: faster energy requirement: slower - peaks in reaction profile: transition state - multistep reactions have many transition states Factors Affecting Rates of Reactions 1. Nature of Reactants - some reactions are inherently fast/slow - dependent on the Ea of the reaction - liquid vs. gas (different phases) - Ea - position in the reactivity series 2. Surface Area - SA, rate - due to the high number of molecules exposed to collision 3. Temperature - T, KE, mobility, frequency of collision, rate - not dependent if the reaction is exothermic/endothermic - Arrhenius Equation - relates rate with temperature - k: specific rate constant 44 | Chemistry 14: Fundamentals of General Chemistry I
4. Concentration of Reactants - Law of Mass Action conc'n, no. of molecules - conc'n, frequency of collision, rate - exception: Zero Order (concentration does not affect rate) Rate Law Expression x y z rate = k [A] [B ] [C ] k = specific rate constant [A] = molar concentration x/y/z = orders of reaction
order of reaction - magnitude of effect of change in concentration zero order: [A]0 = 1 Determination of Order - always experimentally determined and not always = coefficient in balanced equation Method of Initial Rates - given a set of experimental data comparing different rates of reaction - choose one reactant to vary with the other reactants being constant x rateA [A]A = - get the general ratio: rateB [A]B - solve for x to get the order - overall order = (n orders) - with all orders determined, you can find the value of k. 5. Presence of Catalyst - a substance that increases the rate of the reaction without itself being consumed Types of Catalysis: 1. Homogenous - reactants and catalysts are dispersed in the same phase intermediate: valleys in the reaction profile 2. Heterogenous - reactants and catalysts are not of the same phase Example: catalytic hydrogenation - the only factor that affects activation energy - catalysts lower the activation energy - catalysts change the reaction into a multi-step reaction with lower Ea
Chemical Equilibrium
Molecular Equilibrium Definitions Kinetic Definition: rate of forward reaction = rate of backward reaction In a reversible reaction: aA(g) + bB(g)
a b
cC(g) + dD(g)
Kf [A] [B ] = Kb [C ] [D] Rate Laws:
In equilibrium, we assume order is equal to coefficient

PC c PD d P A a PB b
Then, Keq = KC =
Kf [ C ] c [ D ]d = Kb [A]a [B ]b
KP =
Thermodynamic Definition: G = 0
G = G + RT lnQ
Q = reaction quotient
| 45
Q=
[ C ] c [ D ]d [A]a [B ]b
at equilibrium: 0 = G + RT lnKeq G lnKeq = RT Keq = e

G RT
Types of Equilibrium: 1. Homogenous Equilibrium - reactants and products are of the same phase [H2 ][I2 ] H2(g) + I2(g) KC = Example: 2HI(g) [HI ]2 2. Heterogenous Equilibrium - reacyants and products are present in different phases CaO(s) + CO2(g) KC = [CO2 ] ; KP = PCO2 Example: CaCO3(g) KC does not include concentration terms of pure solids/liquids
AgCl(s) Ag + (aq) + Cl (aq) KSP = [Ag + ][Cl ] KSP = solubility product constant
KSP is for partially soluble salts

CH3 COOH + H2 O [H3 O+ ][CH3 COO ] Ka = H3 O+ + CH3 COO [CH3 COOH ] - any mixture with acetic acid is always in equilibrium - Ka = acid dissociation constant Kb = base dissociation constant
Factors Affecting Equilibrium Le Chatelier's Principle - when a stress factor is applied to a system in equilibrium, the system will shift to relieve the stress (relieve the balance) factors: changes in concentration, P, V, T, addition of catalyst
2A(g) + B(g) P(g) + heat
Stresses: Addition of A: shift to the RIGHT Addition of B: shift to the RIGHT Addition of P: shift to the LEFT P (resulting in V) shift ot the RIGHT P, shift to the lesser number of moles) T: shift to the LEFT T favors endothermic processes
Removal of A: shift to the LEFT Removal of B: shift to the LEFT Removal of P: shift to the RIGHT P (resulting in V) shift to the LEFT P, (shift to the higher number of moles) T shift to the RIGHT T favors exothermic processes
catalyst: no shift in equilibrium, they affect both the forward and backward reactions Example:
F e3+ + CN S
orange colorless
F eCN S 2+
blood red
Stresses: Addition of Fe(NO3)3: darker ([Fe3+]) Addition of KSCN: darker ([CNS-]) Addition of AgNO3: Ag+ + SCN- AgSCN (white precipitate) LEFT ([CNS-]) Addition of NaF: lighter (forms FeF63-) ([Fe3+]) Addition of KCl: lighter (forms FeCl63- ([Fe3+]) or by dilution) or no shift: KCl does not react with the species
CH3 COOH + H2 O H3 O+ + CH3 COO
46 |
Stresses: Addition of NaCH3COO: NaCH3COO Na+ + CH3COO- LEFT (common-ion effect: presence of a common ion suppresses the ionization of an electrolyte) Addition of HCl: HCl H+ + Cl- LEFT (common-ion effect) Addition of NaOH: NaOH Na+ + OH- (neutralizes H3O+) RIGHT Addition of NaCl: no shift
CaCO3(g) CaO(s) + CO2(g)
Stresses: Addition of CO2: LEFT Addition of CaO: no shift (solid, is not involved in Keq) Addition of Inert Gas (constant V): PTOTAL Finding KC from equilibrium concentrations
1. Given: CO(g) + Cl2(g) COCl2(g) Cl2 : 0.054M COCl2 : 0.14M Equilibrium Concentrations: CO : 1.2 104 M KC =
(0.14M ) [COCl2 ] = = 216.05 [CO][Cl2 ] (1.2 104 M )(0.054M ) 2HI(g) I2 : 2 103 M
2. Given: H2(g) + I2(g)
Equilibrium Concentrations: HI : 1.87 103 M ICE table I C* E H2 1 103 M -x M 1 103 x M I2 2 103 M -x M 2 103 x M
Initial Concentrations: H2 : 1 103 M
HI 0M +2x M 2x M
*C-row follows stoichiometric coecient [HI ] = 1.87 103 M = 2x
[H2 ] = 1 103 9.35 104 M = 6.5 105 M
x = 9.35 104 M
[I2 ] = 2 103 9.35 104 M = 1.065 103 M KC = (1.87 103 M )2 [HI ]2 = = 50.51 [H2 ][I2 ] (6.5 105 M )(1.065 103 M )
Finding equilibrium concentrations from KC

3. Given: H2(g) + I2(g) 2HI(g) Initial Concentrations: H2 : 1mol KC = 50.5 H2 1M -x M 1-x M I2 2M -x M 2-x M HI 0M +2x M 2x M [HI ]2 I2 : 2mol in 1.0L [H2 ][I2 ] (2x)2 50.5 = (1 x)(2 x) KC = x = 2.92
I C E
46.5x2 151.5x + 101 = 0 x = 0.93
[HI ] = 2 0.93 = 1.86M [H2 ] = 1 0.93M = 0.07M [I2 ] = 2 0.93M = 1.07M
| 47
4. Given: COCl2(g)
CO(g) + Cl2(g)
KC = 1.19 1010 Is the system in equilibrium? QC =
Initial Concentrations: COCl2 : 3.50 103 M CO : 1.11 105 M Cl2 : 3.25 106 M
(1.11 105 M )(3.25 106 M ) [CO][Cl2 ] = = 1.19 108 [COCl2 ] (3.50 103 M )
Note: If KC > QC , there are more reactants than in equilibrium (forward shift) If KC = QC , there is equilibrium If KC < QC , there are more products than in equilibrium (backward shift) KC < QC , therefore, there is no equilibrium COCl2(g) 3.50 103 M +x M 3.50 103 + x M CO(g) 1.11 105 M -x M 1.11 105 x M Cl2(g) 3.25 106 M -x M 3.25 106 x M
I C E
KC =
x = 1.12 105
[CO][Cl2 ] [COCl2 ] (1.11 105 M )(3.25 106 M ) 1.19 1010 = (3.50 103 M ) x = 3.15 106
[CO] = 7.95 106 M [Cl2 ] = 1.00 107 M
[COCl2 ] = 3.50 103 M
Ionic Equilibrium - between weak acids and weak bases - any solution of a weak acid or a weak base is in equilibrium
[H3 O+ ][CH3 COO ] CH3 COOH + H2 O H3 O + CH3 COO [CH3 COOH ] Ka = acid dissociation constant
+
Example 1:
Ka =
Ka for CH3COOH = 1.8x10-5 - it is a small value, which means that the concentration of the products is much less than the concentration of the reactants Example 2:
[N H3 OH ][OH ] Kb = [N H3 ] N H3 + H2 O N H4 + + OH Kb = base dissociation constant Kb for NH3 = 1.8x10-5
Ka from % ionization
1. Given: HA + H2 O H 3 O + + A
0.010 M HA; 2.0% ionization HA 0.01 M -(0.020.01) M H3 O+ A Chemistry 0M 0 14: M Fundamentals of General Chemistry I +(0.020.01) M +(0.020.01) M
48 |
I C
1. Given: HA + H2 O
H3 O + A
0.010 M HA; 2.0% ionization HA 0.01 M -(0.020.01) M 9.8 103 M H3 O+ 0M +(0.020.01) M 2 104 M A 0M +(0.020.01) M 2 104 M
I C E
Ka =
(2 104 M )(2 104 M ) [H3 O+ ][A ] = = 4.08 106 [HA] (9.8 103 M )
% ionization from Ka
2. Given: CH3 COOH + H2 O H3 O+ + CH3 COO 0.010 M CH3 COOH; Ka = 1.8 105 CH3 COOH 0.01 M -x M 0.01-x M H3 O+ 0M +x M xM CH3 COO 0M +x M xM
I C E
Ka =
[H3 O+ ][CH3 COO ] [CH3 COOH ] (x)(x) 1.8 105 = 0.01 x C 100, then you can round o Keq
Rounding o: If Therefore: 1.8 105 = x=
= 4.24 104 = [H3 O+ ] 4.24 104 ionized f orm 100 = 100 = 4.24% unionized f orm 0.01 Note: kay sir Quiming lang yata pwede yung round-off thing %ionization =
x2 0.01 (1.8 105 )(0.01)
pH = log [H3 O+ ]
autoionization of H2 O: H2 O + H2 O at 25 C, [H3 O+ ] = [OH ] = 1.0 107 M KW = equilibrium constant for H2 O = [H3 O+ ][OH ] = (1.0 107 M )(1.0 107 M ) = 1.0 1014
pOH = log [OH ]
H3 O+ + OH
logKW = log [H3 O+ ] + log [OH ] 14 = pH + pOH
1. pH of strong acids and bases: HCl H+ + Cl full ionization

Given: 0.1 M of HCl pH = log [0.1M ] = 1
| 49
2. pH of weak acids and bases Given: HCN + H2 O H3 O+ + CN

0.2 M HCN; Ka = 4.9 1010 HCN 0.2 M -x M 0.2-x M H3 O + 0M +x M xM CN 0M +x M xM
I C E
[H3 O+ ][CN ] [HCN ] (x)(x) 4.9 1010 = 0.2 x Ka = 0.2 100, therefore you can round o 4.9 1010 x2 4.9 1010 = 0.2 x = (4.9 1010 )(0.2) = 9.90 106 = [H3 O+ ]
pH = log [H3 O+ ] = 5.00
= log (9.90 106 M )
Note: if roundable: pH = -log Ka C
3. Salts: formed by an acid plus a base a. Strong Acid + Strong Base = Neutral Salt Example: HCl + N aOH N aCl + H2 O Na+ is a metal Cl- is a very weak base (conjugate of a very strong acid) b. Weak Acid + Strong Base = Basic Salt Example: CH3 COOH + N aOH N aCH3 COO + H2 O Na+ is a metal CH3COO- : CH3 COO + H2 O CH3 COOH + OH c. Strong Acid + Weak Base = Acidic Salt Example: HCl + N H4 OH N H4 Cl + H2 O NH4+ : N H4 + + H2 O N H3 + H3 O+ Cl- is a very weak base (conjugate of a very strong acid) d. Weak Acid + Weak Base = Acidic/Basic/Neutral - it is dependent on the Ka of the acid and the Kb of the salt Ka = Kb, Neutral Salt CH3 COOH + N H4 OH N H4 CH3 COO + H2 O Example: Ka of CH3 COOH = Kb of N H4 OH Ka > Kb, Acidic Salt Ka < Kb, Basic Salt
50 |

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CHEMISTRY 14

The Fundamentals of General Chemistry I

Prof. Noel S. Quiming Department of Physical Sciences and Mathematics

Chemistry 14: Fundamentals of General Chemistry I

Prof. Noel S. Quiming

where: A is the mass no. and Z is the atomic no.

H (protium) H (deuterium) H (tritium)

Chemistry 14: Fundamentals of General Chemistry I

Rh = Rydberg constant = 2.1 1018 J

= 3.0 108 m/s

Prof. Noel S. Quiming

Possible Values positive integers (1, 2, 3, ...)

n=1 n=2 n=3 n=4

l=1 l=2 l=3

m = -1, 0, +1 m = -2, -1, 0, +1, +2 m = -3, -2, -1, 0, +1, +2, +3

2s: Ground state: 1s:

2s: Ground state: 1s: 2s: _ Excited state: 1s:

2p: _ _ _ 2s: Ground state: 1s: Differentiating Electron: (2, 1, +1, -)

2p: _ _ 2s: Ground state: 1s: Differentiating Electron: (2, 1, +1, -)

Differentiating Electron: (5, 1, +1, -)

[He]2p63s23p6 3p: (Stable) [He]2p63s23p3 3p: _ _ _ [He]2p63s23p4 3p: _ _

Stability: Ar > P > S Cu: [Ar]4s23d9 [Ar]4s13d10

4s: 3d: _ 4s: _ 3d:

(LESS STABLE) (MORE STABLE)

Pseudo-Noble Gases Zn: [Ar]4s23d10 30 Zn2+: [Ar]4s03d10 30

The Chemical Bond

#e 26 24 23 Fe > Fe2+ > Fe3+

p/e 1 1.08 1.13

p/e 1.1 1.2 1.3 N3O

p/e 0.7 0.8 0.9

2. No. of valence electrons available: 3. No. of shared electrons: 4. No. of bonds:

17 valence electrons 24-17 = 7 electrons 7/2 = 3.5 bonds

ES: 6s: _ 6p: _ __ __ (forms 2 covalent bonds)

(forms 4 covalent bonds) TETRAHEDRAL molecular geometry bond angle: 109.5

TRIGONAL BIPYRAMIDAL molecular geometry bond angle: 120 (equatorial) 90 (axial)

OCTAHEDRAL molecular geometry bond angle: 90

TRIGONAL PYRAMIDAL molecular geometry bond angle: <109.5 ( 107) or TRIPOD

HS: sp3d2: _ _ _ _ _ (forms 5 covalent bonds and 1 lone pair)

Prof. Noel S. Quiming

O2, F2, Ne2

B2, C2, N2 *: __ p*: __ __ INCREASING ENERGY

FW of Ca3 (P O4 )2 : Ca : 3 40.01 = 120.03 P : 2 30.97 = 61.94 O : 8 16.00 = 128.00 = 309.97 amu

Chemistry 14: Fundamentals of General Chemistry I

Examples: Needed: atoms in 4.21 mol of Pt

= 1.02 1024 atoms H

Percent Composition - percent by mass of each element in a compound

Prof. Noel S. Quiming

Empirical Formula based on % Composition

Chemistry 14: Fundamentals of General Chemistry I

EF : CO2 F2 CO2 F2 : 12.01 + (2 16.00) + (2 19.00) = 82.01g/mol 82 1 f= 82.01 M F : CO2 F2

Prof. Noel S. Quiming

Mole-Mole Conversions 1. Given: 2N a + Cl2 2N aCl 2.6 molCl2

Mole-Mass Conversions 1. Given: 2N a + Cl2 2N aCl || 5 molN a

70.90 gCl2 1 molCl2

Mass-Mole Conversions 1. Given: 2C2 H6 + 7O2 4CO2 + 6H2 0 || 10.0 gH2 O

Mass-Mass Conversions 1. Given: N2 + 3H2 2N H3 || 2.00 gN2

2. Given: 2N a + I2 2N aI || 93.25 gI2 gN aI = 93.25 gI2 1 molI2 253.8 gI2

Chemistry 14: Fundamentals of General Chemistry I

32.00 gO2 1 molO2

601gF e2 O3 366.99gF e2 O3 = 234.01gF e2 O3

Prof. Noel S. Quiming

gT i = 3.54 107 gT iCl4 gT i = 1.13 107 gM g b. % yield =

7.91 106 gT i 8.93 106 gT i

56.01 gCaO 1 molCaO

ES: 6s: _ 6p: _ (forms 2 covalent bonds)

B2, C2, N2 : p: __ INCREASING ENERGY