Chem 16 Notes

UPD
Should only be a supplement to discussions

Table of Contents*
[A] Lecture
[1] Thermodynamics
[2]Energy
[3]Enthalpy
[4]Hess's Law
[5]Determining Enthalpy
[6]Heat Capacity
[7]Calorimetry
[8] Entropy
[9] Gibb's Free Energy
[10] Waves
[11] Quantum Theory
[12] Quantum Numbers
[13] Electron Configuration
[14] Periodic Table
[15] Periodic Trends
KSev

[16] Chemical Bonding

[17] Formal Charge
[18] Resonance Structure
[19] Bonds
[20] VSEPR
[22] Valence Bond Theory
[22] Molecular Orbital Theory
[B]Lab
[1] Corrosion
[2] Oxidation Reduction Reactions
[3] Calorimetry
[4] Qualitative Analysis
[5] Flame Test
[6] Molecular Model
*(Ctrl + F the roman numeral to skip to
that part. Ex: [B.3])

KSev

[A.1] Thermodynamics
Thermodynamics
thermo = heat
dynamics = movement
It has 3 parts
system
the object being observed
surroundings
everything not part of the system
boundary
the division between system and surrounding
Universe
the sum of the 3 parts
Internal Energy
energy found within the universe
sum of all Potential Energy (PE), Kinetic Energy (KE), and energy is general
E=E finalE init= E productE reactant

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[A.2]Energy
Energy
capacity for heat and/or work
heat
symbolized by q
movement of energy due to the difference in temperature
when a system is cold, it means it has a higher temperature and the heat is leaving
the system
When a system is hot, it means the surrounding has a higher temperature and the
heat is entering the system
work
symbolized by w
can done by or to the system
When work is done by the system, there is a release of energy
When work is done to the system, there is an absorption of energy
E=q+w
sign depends on change
+q = endo
-q = exo
Properties of Energy
1st Law
energy is constant
E univ= E sys+ E surr =0
SI unit is Joules (J)
[(kg)(m)2 ]
1
s2

1 cal = 4.184 J
Capital Letter(Cal) = kilo (kilocal)
State function
doesn't care on process, just endpoint
work, not power

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[A.3]Enthalpy
Enthalpy
symbolized by H
heat gained/lost at a constant pressure
H =q= E+P V
heat of reaction
state function
can be + or magniture of heat = proportional to the amount of substance
measured in kJ/mol

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[A.4]Hess's Law
Hess's Law
enthalpy change is the sum of the enthalpy of individual steps
H total = H 1+ H 2 +...
In the case that the reaction needed is happening in the opposite direction (you want the
product but it is in the reactant,etc.)
To reverse the reaction, one must simply get the negative of the H

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[A.5]Determining Enthalpy
Determining Enthalpy
0
0
H rxn= m H [ f ( product )]n H [ f (reactant )]
m/n
number of moles
Standard Heat of Formation
symbolized by H0f
enthalpy change for the formation equation when substances are in their standard state
stable = neutral = 0
Determined at 1 atm, 25oC, 1M
Measuring Heat of Reaction
heat is proportional to T
q=k T

KSev

[A.6]Heat Capacity
Heat Capacity
heat required to change temperature by 1K/10C
q
J
=
( T ) K
Specific Heat
heat required to change the temperature of 1g by 1K/10C
q
J
c=
=
[(mass)( T )] gK

Molar Heat
heat required to change the temperature of 1 mol by 1K/10C
q
J
C=
=
[(mole)( T )] molK

KSev

[A.7]Calorimetry
Calorimetry
measures the heat
types
constant pressure
styro
coffee cup
constant volume
bomb
assumes no heat exits the universe
adiabatic system
useful solutions
q sys=q surr
the heat released is the heat absorbed
q=mc T
q cal =C cal T
q=n LR H
q rxn=( qcal +q H2O)

KSev

[A.8] Entropy
Spontaneity
changes happening without continuing outside influence
Entropy
measure of chaos, disorder, or randomness in a system
Meaning
S >0
increases
favors spontaneity
S <0
decrease
does not happen spontaneously
S =0
only occurs at 0K
means nothing is occuring
S
=S
univ
sys +S surr >0

S gas > S liquid > S solid

Predicting Entropy
Change in # of Particles
if there is an increase
S sys>0
Change in # of moles in Gaseous substance
if there are more gaseous substances
S sys>0
Values
reference state is 0K, Absolute Zero

J
molK

Solving

S 298= n S product n S reactants

2nd Law
S >0
G >0
Aspects
exothermic (H) does not ensure spontaneity
S does not ensure spontaneity
KSev

[A.9] Gibb's Free Energy

Gibb's Free Energy
energy released to surrounding
reliable indicator of spontaneity
Meaning
negative(-) means spontaneous
positive (+) means non spontaneous
0 means equillibrium
Stable
0
G =0
Solved at 250C, 1 atm
same as Enthalpy
0

G 298 = m G product n G reactants

don't SF, constant (same w/ Hess)
Free Energy Calculation
G = H T S
Gatas Equation
constant temperature and pressure
goal is -G
since that would be spontaneous

KSev

[A.10] Waves
Wave
frequency,f
cycles/sec
length,
distance from 2 crests
Visible Light
400-750 nm
Speed of Light, c
3 x 108 m/s
f
Wave-particle duality of light
Light acts as both a wave and a particle
Notable Equation for solving with waves

E=mc2=hf =

hc

E is energy
m is mass
c is speed of light
h is Planck's constant ( 6.626 x 10-34 Js or kgm^2/s)
is wavelength

Heisenberg's Uncertainty Principle

can't know speed AND location

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[A.11] Quantum Theory

Quantum Theory
atoms only exist in certain energy levels
atoms emit or absorb light as they change states
allowed energy elevels, described by number
This serves as the basis for how we understand the quantum world

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[A.12] Quantum Numbers

Quantum Numbers
n, principal
level or shells
+1,2,...
l, angular momentum
subshell, shape
0,1,...,(n-1)
ml, magnetic moment
orientation
-l,..., 0,..., +l
ms, spin
spin of the electron
either + or
Pauli's Exclusion Principle
no two electrons can have the same quantum numbers

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[A.13] Electron Configuration

Electron Configuration
distribution of electrons in atom in orbitals
Placement and Arrangement
2 electrons at rest per orbital
for degenerate, place electron alone first
Aufbau Principle
building up
orbitals are arranged in increasing energy
n value, energy
generally s < p < d < f
Hund's Rule
when writing electrons, write the electrons alone first before pairing up
Writing Electron Configuration
Shorthand
(n)(l)number of electrons
Orbital Diagram
Drawing Boxes and Stuff
Can be used to determine magnetism
Paramagnetic
attract
at least 1 unpaired e odd
#e- mod value of last orbital
Diamagnetic
repel
all paired
Group 2A/2, Group 2B/12, Group 8A/18
Condensed
Noble Gas + EC
NOTE
Cr and Cu
only have 4s1
remove if cation
since it is still the outermost
higher stability
less repulsion if inner is completed

KSev

[A.14] Periodic Table

Definition of Terms
S-block, P-block, D-block, F-block
how the periodic table is arranged
Group 1A
Alkaline Metal
Group 2A
Alkaline Earth
Group 6A
Chalcogens
Group 7A
Halogens
Group 8A
Noble Gas
Isoelectronic
same number of e Downwards
group
Across
period

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[A.15] Periodic Trends

Periodic Trends
Size (Atomic and Ionic)
Down a group
increase
Across a period
decrease
Ionic
negative is larger
Ionization Energy
energy needed to remove one e >0
Down
decrease
Across
increase
Electron Affinity
energy needed to add an electron to an isolated gas
energy released
<0
Down
decrease
Across
increase
Electronegativity
attract e Most electronegativity F
Down
decrease
Across
increase
Metallic Behavior
behavior to lose an electron
Down
increase
Across
decrease

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[A.16] Chemical Bonding

Chemical Bonding
used by elements to help achieve 8 valence electrons
Ionic
Metal + Non-metal
Electron Transfer
Covalent
Non-metal + Non-metal
Electron Sharing
Metallic
Metal + Metal
Sea of Electrons
LEDS
Drawing the valence electrons about a chemical's symbol
bonding
octet rule, usually
there is a duet rule, incomplete octet, and expanded octet rule
if there is a charge, place in a bracket and write charge in upper right
Ionic
just write the charge next to the elements
no lines, just the symbols next to each other
Covelent
H is an exception to the octet rule in that it needs only 2 electrons
2 shared electrons
shown by line
can be bond, double bond, or triple bond
Steps for n < 3
determine the central atom
it is the least electronegative
count e- needed to complete
count total available e( Needed eavailable e)
(e shared )
=Number of Bonds=
2
2

Distribute remaining

KSev

[A.17] Formal Charge

Formal Charge
charge of molecule/ion
number associated to each atom in the LEDS
negative goes to the more elctronegative atoms (and so not the central)
though that would mean the central atom can become positive
Solving for Formal Charge
Group # - (Dots + Lines)
aim is zero for most, if not all

KSev

[A.18] Resonance Structure

Resonance Structure
bonding all possible
LEDS where there is a possibility for multiple different ways of bonding
The changing of which atom the double bond is found is not a result of rotating the
molecule
it is different atoms possibly double bonding with the central atom
shown by double-headed arrows leading to the different structures
Resonance Hybrid
Average of all resonance structures
dotted lines to denote incomplete/shared bonds
no dots
Exceptions in LEDS
Duet Rule
H and He
Incomplete Octet
less than 8 valence electrons
3A, B, Be, Odd e Expanded Octet
more than 8 valence electrons
elements where n greater than or equal to 3
this is due to allowing the extra electrons to ending the d-orbital or f-orbital
Formal Charge > Octet
- prioritize formal charge over octet rule in determining stability
Bond Order Bond Energy

1
(bond length)

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[A.19] Bonds
Bond Polarity
determined by EN
Non Polar
=0
Polar
not equal to Zero
Can simply be determined if same element or not
except for C and H
since they have nearly the same electronegativity
meaning when they bond, it is non polar
H rxn= BE

Positive
endothermic
Negative
exothermic
Bonds
Breaking
positive
there is a release of energy
Forming
negative
use energy to form the bond
When in gaseous states,HCl is bonded

KSev

[A.20] VSEPR
Valence Shell Electron Pair Repulsion (VSEPR)
shapes
arrangement of e- domains
determines polarity
Strongest repulsion is lone-lone, then lone-bond, then bond-bond
Electron Group Geometry
e- pairs arrangement
Molecule Group Geometry
molecule arrangement
Electron Group Geometry
Number of Pairs

Shape

Angles in degrees

Linear

180

Trigonal Planar

120

Tetrahedral

109.5

Trigonal Pyramidal

90, 120

Octahedral

90

Look

Molecular Group Geometry

Number of Pairs

Lone Pairs

Shape

Linear

Bent

Linear

Trigonal Pyramidal

Bent/Angular

Seesaw

T-shaped

Linear

Square Pyramid

Square Planar

T-Shaped

Linear

4
5

Look

When there are no lone pairs, EGG = MGG

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[A.21] Valence Bond Theory

Valence Bond Theory
covalent bonds formed by overlap of atomic orbitals
hybridization
S orbit + P + D +
needs to be single to be able to bond
count e- groups
Basis of Hybrid = # of e- groups = EGG
Sigma () bonds are head-on
Pi () bonds are sideways
Cheat sheet
1 bond = 1 sigma
Double Bond = 1 Sigma, 1 Pi
Triple Bond = 1 Sigma, 2 Pi

KSev

[A.22] Molecular Orbital Theory

Molecular Orbital Theory
Atomic orbitals combine to become molecular orbitals
Number of Molecular Orbitals forward =Number of Atomic Orbitals combined
= head on bonding; * = anti-bonding
= sideways bonding; * = anti bonding
Star is higher energy
Written = 1s*1s
s = only sigma bonds
p= 1 sigma, 2 pi
Sigma bonds have 2 electrons while Pi bonds have 4
Still follow lowest energy to highest
Can be
B,C,N
1s*1s2s*2s2p2p*2p*2p
O,F,Ne
1s*1s2s*2s2p2p*2p*2p
Order can change
due to the similar levels of energy of pi 2p and sigma 2p
(Number of Bonding eNumber of Anti bonding e )
2
Bond Order:

KSev

[B.1] Corrosion
Experiment 6
Corrosion
observinig a form of redox reaction
a reaction where the nail is attacked and lost in various reactions
Results
Straight Nail
Center is pink
Tip and Head are blue
Bent Nail
Tip, point of stress, and head are blue
pink around
Nail with Zinc
white near Zinc
Nail with Copper Wire
Pink center
Tip and Head are blue
Copper Wire is unaffected
Explanation
Straight
+2
1
Fe Fe +2 e
oxidize, anode

O 2+ H 2 O+4 e 4OH

reduce, cathode

+2

Fe + Fe( CN )6 Fe3 [ Fe( CN )6 ]2

Turnbull's blue

OH 1+Phth Pink

Obviously, Phenolphthalein pink

blue due to stress
Bent
strained
more active, more anodic
Nail with Copper
same since Copper didn't affect redox
Fe > Cu in reducing property
Nail with Zinc
+2
1
Zn Zn +2 e
oxidize, anode

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+2

Zn +OH

Zn + Fe (CN )6 Zn3 [ Fe(CN )6 ] 2

+2

Zn(OH )2
3

both are white precipitate

Zn > Fe in reducing property
In the end
Zn > Fe > Cu in reducting property
Things to Learn
Reducing Property
Using indicators as a way to tell the reaction has occurred
Special Notes
Chemists were also Painters
that's why they named the reactions as colors and so
Prussian Blue = the blue the Prussians wore
Red Lake = the red used to paint lakes...?
Anode
Where oxidation occurs
An Ox
Cathode
where reduction occurs
Red Cat

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[B.2] Oxidation Reduction Reactions

Experiment 5
Oxidation Reduction Reaction
learning about Redox Reactions
learning about oxidation or reducing property
Since areaction will occur with a visible change, that is the basis for the follow
experiment
Reduction
gain e lower/reduce Oxidation Number
GEROA
Oxidation
loss e increase in Oxidation Number
LEORA
Results
seen on the following pages
Things to Learn
Oxidizing and Reducing Property
Difference in Product based on Environment
How to Solve Redox/Net Ionic Reactions
Special Notes
Some products are more available depending on the medium
Acidic
H+, H2O
Basic
OH-, H2O

Cu

Fe

Cu2+

Fe2+

Zn2+

H+

No Change

No Change

No Change

2+

2+

Fe > Cu

Zn > Cu

H2 > Cu

Metal rust
Solution - yellow

No Change

Metal corrodes
Solution - Bubbles

Fe + Cu2+ Cu +
Fe2+

Fe + Zn2+ Fe +
Zn2+

Zn + 2H+ Fe2++
H2

Fe > Cu

Zn > Cu

Fe > H2

Cu + Fe NVR Cu + Zn NVR Cu + 2H+ NVR

KSev

Zn

Metal from silver

to black
Solution From
blue to greenish

Metal turned
black
Solution light
yellow

Bubbles

Zn + Cu2+ Cu +
Cu2+

Zn + Fe2+ Fe +
Zn2+

Zn + 2H+ Zn2++
H2

Zn > Cu

Zn > Fe

Zn > H2

Reactivity Series: Zn > Fe > H2 < Cu

Br2

I2

Cl-

Br-

I-

Organic(org) Turned
Yellow
Aqueous(aq)
Colorless

Org Yellow
Aq Yellow

No Reaction

Br2 + 2I- I2+ 2Br-

Cl > Br2

Br2 > I

Org Pink
Aq - Colorless

Org Pink
Aq - Yellow

No Reaction

No Reaction

Cl > I2

Br > I2

Reactivity Series: Cl2 > Br2 > I2

Cl-

Aq is Colorless

Cl2

Org is Colorless

Br-

Aq is Yellow

Br2

Org is Yellow

Aq is Yellow

I2

Org is pink

SO32- + MnO4 Neutral

2MnO4- + 3SO32- + H2O 2MnO2+ 3SO42- + 2OH MnO2 is brown ppt
Acidic
2MnO4- + 3SO32- + 6H+ 2Mn2++ 5SO42- + 3H2O
Colorless
Basic
2MnO4- + SO32- + 2OH- 2MnO42- + SO42- + H2O
auto dissociation

KSev

[B.3] Calorimetry
Experiment 8
Calorimetry
heat measurement
system + surrounding = universe
seperated by a wall
Exothermic = negative H
Endothermix = positive
When Pressure is constant, this is a coffe cup calorimeter and solves for H
When Volume is constant, this is a bomb calorimeter and solves for E
Using a coffe cup calorimeter, seeing reactions and changes in temperature due to them
Can be used to solve for heat, specific heat, temperature change,etc
Notable Equations
J
q=(m)(c)( T )=(C cal )( T )=(m water )( 4.18
)( T )
gC

or more specifically with the experiment

J
mc T =[C cal T +mwater 4.18
T ]
gC

q rxn+q H20 +q cal =0

Matter

Energy

Open

Permeable

Permeable

Closed

Impermeable

Permeable

Diathermal

Isolated

Impermeable

Impermeable

Adiabatic

Things to Learn
Solving Calorimetry problems
Special Notes
Thermometer
part of the surroundings
if an increase in temp is noted, it is exothermic
because the surround absorbed the energy released by the system(the reaction)
Theoretical H for Neutralization Reactions = -55.85 kJ/mol

KSev

[B.4] Qualitative Analysis

Experiment 11
Qualitative Analysis
to observe various reactions and use qualities to define elements
doesn't care about quantity like how much substance but instead if the substance is
present or not
Quantitative numerical value/amount
Qualitative test of Presence
Classical
has a limit of detection at .1M
Instrumental
spectrometer
Tests
Elimination
allows you to group the elements
Confirmatory
allows you to identify
Results
seen in the following pages
Things to Learn
- being able to tell the presence of elements based on qualities such as color and acidity
Cations Test
Add NaOH
Blue ppt

Brown Ppt

White Ppt

Nothing

Copper

Iron
(Yellow Sol'n)

Calcium OR Zinc
(Zn is sparingly soluble)

Ammonia

Cu2+ + 2(OH)- Fe3+ + 3(OH)- Ca2+ + 2(OH)- Zn2+ + 2(OH)- NH4 + + OH- NH3 + H2O
Cu(OH)2
Fe(OH)3
Ca(OH)2
Zn(OH)2
Add Excess NaOH
PPT remains

PPT dissolves
Zn(OH)2 + 2OH [Zn(OH)4]2-

Add NH3
Blue Ppt

Brown Ppt

White Ppt

Nothing

Copper

Iron

Zinc

Calcium OR Ammonia

Cu2+ + 2(OH) Cu(OH)2

Fe3+ + 3(OH)- Zn2+ + 2(OH)-

Fe(OH)3
Zn(OH)2

Ca
Weak OH, soluble

NH4 + + OH- NH3 +

H2O
KSev

Add Excess NH3

Deep Blue

White Solution

Cu(OH)2 + 4NH3
[Cu(NH3)4]2+

Zn(OH)2 + 4NH3
[Zn(NH3)4]2+

Confirmatory Test
Copper

Cu2+ + NH3 [Cu(NH3)4]2+

Blue

Iron

Fe + SCN

Blood Red Complex

Calcium

Ca + C2O4
2+

Zinc

Ammonia

White ppt
3-

Zn + Fe(CN)6
Zn3[Fe(CN)6]2

Yellow ppt

Zn2+ + Fe(CN)64-
Zn2[Fe(CN)6]

White ppt

NH4+ + OH- NH3 + H2O

Evolution of Gas
Red Litmus to Blue

Anions Test
Add HNO3 and Ba(NO3)2
Add Fe3+
Ppt

Pink Organic

Blood Red
Aqueous

Nothing

Carbonate OR Phosphate OR Sulphate

Iodine

Thiocynate

Bromine OR Nitrate

Ba2+ + CO32- Ba2+ + PO43- Ba2+ + SO42- 2I- I2 + 2e

BaCO3 Ba3(PO4)2 BaSO4
Add Acetic Acid

Fe3+ + SCN

[FeSCN]2+

(Use new sol'n with HNO3 and Ba(NO3)2) Add KMnO4

Ppt
disappears,
bubbles

Ppt
disappears

Ppt remains Pink Organic

Carbonate

Phosphate

Sulphate

BaCO3 +
2OAc
Ba(OAc) +
H2CO3

Ba3(PO4)2 +
6OAc
Ba(OAc) +
2H3PO4

BaSO4 +
2OAc
Nothing

Iodine

Yellow
Organic

Nothing

Bromine

Thiocynate OR Nitrate

2I I2 + 2e 2Br Br2 +
2e

KSev

Confirmatory Test for Nitrate

Sol'n + 1 drop 6M sulfuric + 3 drops Fresh Iron Sulfate + 2 drops 18 Sulfuric
Evolution of Heat is NOT an indicator
Dilution of Sulfuric Acid always results in the evolution of heat

KSev

[B.5] Flame Test

Experiment 9
Flame Test
igniting various compounds to see the color released
a form of qualitative analysis in that the color released reflects the element contained
a way of showing what happens when energy is absorbed and thus released
Motion from the ground state to the excited state and back
Useful Equations
E=

hc

2
E=mc
f =c
Note
h=6.626 x 1034 ( J ) s

[(kg ) m ]
s

8
c=3 x 10 m/s
Visible Light's wavelength is within 400-750 nm( 1 x 10-9)
Results
Substance

Color of Flame

H 2O

None

NaCl

Red

CaCl 2

Yellow

CuCl 2

Blue Green

KCl

Violet/Purple

BaCl 2

Yellow-Green

Things to learn
Solving problems regarding the equations above

KSev

[B.6] Molecular Model

Experiment 12
Molecular Model
using sticks and clay to represent molecular compounds
visualization of how these compounds are shaped
application of VSEPR
Things to learn
How to solve
Number of Valence Electrons
group number
LEDS
Formal Charge
Resonance Structure
EGG
MGG
Sigma Bonds
Pi Bonds
Bond Angles
Bond Length
Bond Polarity
Hybridization
Polarity of the Molecule
if charged, polar because it means it's soluble in water
dissociation
OverlappingValence Orbitals

KSev