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ANYTHING!!!!!!!
KEEP TRACK OF/WRITE THE NUMBER OF SIGNIFICANT FIGURES NEAR THE ANSWER SO
THAT YOU CAN USE THEM AS REFERENCE FOR THE FINAL FINAL ANSWER BUT DO NOT
ROUND OFF IF THE ANSWER IS STILL GOING TO BE USED.
INCLUDE UNITS IN CALCULATIONS
SIGNIFICANT FIGURES
Kc (FOR EQUILIBRIUM)
Aa + Bb -> Cc + dD
[𝐶]𝑐 [𝐷]𝑑
𝑘𝑐 = → 𝐿𝑎𝑤 𝑜𝑓 𝑀𝑎𝑠𝑠 𝐴𝑐𝑡𝑖𝑜𝑛
[𝐵]𝑏 [𝐴]𝑎
𝑘𝑐 → 𝐶𝑜𝑛𝑡𝑠𝑎𝑛𝑡 𝑎𝑡 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑡𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒
(NO SOLIDS AND PURE LIQUIDS!!!) Expressions for Equilibrium
constant (Kc)
If PRESSURES ARE GIVEN
𝑃𝐶 𝑐 × 𝑃𝐷 𝑑
𝑘𝑝 =
𝑃𝐵 𝑏 × 𝑃𝐴 𝑎
1
1) When a rxn has Kc1: if the rxn is reversed Kc2=
𝐾𝑐1
2) When a rxn has Kc1: if the rxn is multiplied by “X” Kc2=(𝐾𝑐1 )𝑋
1
3) When a rxn has Kc1: If the rxn is reversed and multiplied by “X” Kc2=( )𝑋
𝐾𝑐1
4) When rxn 1 (Kc1) and rxn 2 (kc2) are added: Kc3 = 𝐾𝑐1 × 𝐾𝑐2
𝑃𝑉 = 𝑛𝑅𝑇
Add the mole ratios for the products
𝑃 = 𝐶𝑅𝑇
DIRECTION OF RXN
RXN QUOTIENT (Q>> AT ANY POINT)
Aa + Bb -> Cc + dD
[𝐶]𝑐 [𝐷]𝑑
𝑄=
[𝐵]𝑏 [𝐴]𝑎
[𝐶]𝑐 [𝐷]𝑑
𝑘𝑐 =
[𝐵]𝑏 [𝐴]𝑎
Q<K : FORWARD, Eq lies right, high [PRODUCTS]
Q>K: REVERSE, Eq lies left, high [REACTANTS]
Q=K: NEITHER, RXN AT equilibrium, rate forward= rate backward ([products] NOT
NECESSARILY = TO [reactants] )
Eq concentration/pressure
Steps to Solving EQUILIBRIUM Problems:
1. BALANCE EQUATION
2. Write an equilibrium expression for the balanced reaction.
3. Write an ICE table. Fill in the given amounts.
4. Use stoichiometry (mole ratios) on the change in concentration line.
5. Deduce the equilibrium concentrations of all species.
6. Usually, the initial concentration of products is zero. (This is not always the case.)
APPROXIMATION: If Kc*100 < [INITIAL CONCENTRATION FOR A SPECIFIC VARIABLE Y]
then
➢ [Y]Initial -x (at the equilibrium) = [Y] Initial
IF WE DISTURB AN EQUILIBRIUM, THE K value will remain the same FOR THE SAME
TEMPERATURE
Pressure: Atmosphere (atm)
Concentration: Molarity (Mol/L)
M aA bB cC dD
I (M or pressure)
C(M or pressure)
E(M or pressure)
M aA bB cC dD
I (M or pressure)
C(M or pressure)
E1(M or pressure)
Disturbance (a CERTAIN variable added or
removed)
I (M or pressure)
C(M or pressure)
E2 (M or pressure)
LE CHATELIER
- If we disturb a system, the system will act in such a way as to oppose the change
DISTURBANCES
VOLUME
- When the volume of a gas is decreased, the pressure of that gas increases (low
number of moles of gas) and the concentration increases. -> PRODUCT
FAVOURED/FORWARD
- When the volume of a gas is increased, the pressure of that gas decreases (high
number of moles of gas) and the concentration decreases. When volume halves,
pressure doubles. -> REACTANT FAVOURED/BACKWARD
(Increase volume = Pressure decrease = Concentration decreases -> AND VICE VERSA)
TEMPERATURE
- Endothermic: Reactants + ENERGY -> Products
- Exothermic: Reactants -> Products +ENERGY
➢ High Temp = Low value of Kc
IONIZATION CONSTANT (AND AUTOIONISATION OF WATER)
[𝐻3 𝑂+ ][𝐴− ]
For an acidic solution: 𝐾𝑎 =
𝐻𝐴
- 𝐾𝑤 = [𝐻3 𝑂+ ][𝑂𝐻− ]
- 𝐻2 𝑂(𝑙) + 𝐻2 𝑂(𝑙) → 𝐻3 𝑂+ (𝑎𝑞) + 𝑂𝐻− (𝑎𝑞)
Solubility equilibrium constant (Ksp)
Monoprotic acids: Acids such as HF, HCl, HNO3, and CH3CO2H (acetic acid) are all capable
of donating one proton
Polyprotic acids: acids that are capable of donating two or more protons.
Polyprotic bases: bases that can can react more than once with water
- Eg) N2H4, H2NCH2CH2NH2, Na2CO3 (diprotic)
- CO3 2- (aq) + H2O(l) -> OH‐ (aq) + HCO3‐ (aq)
• HCO3 ‐ (aq) + H2O(l) -> OH‐ (aq) + H2CO3 (aq)
- WHEN REACTING THE POLYPROTIC SALTS (BASE OR ACID) MAKE SURE THE
NEUTRAL/NON REACTIVE/SPECTATOR ION IS EXCLUDED
7 Common Strong acids (aq):
- HCℓ
- HBr
- HI
- HNO3
- H2SO4
- HClO4
- HClO3
Ka for weak acids<1
Autoionization of Water (ion-product constant)
- 𝐾𝑤 = [𝐻3 𝑂+ ][𝑂𝐻− ]
𝐾𝑤
➢ −
= [𝐻3 𝑂+ ]
[𝑂𝐻 ]
➢
- 𝐻2 𝑂(𝑙) + 𝐻2 𝑂(𝑙) → 𝐻3 𝑂+ (𝑎𝑞) + 𝑂𝐻− (𝑎𝑞)
- At 25C Kw = 1.0 10−14
• Neutral [H+] = [OH− ] = 1.0 10−7 M
• Acidic [H+] > [OH− ]
• Basic [H+] < [OH− ]
pH (equilibrium)
- pH = − log [H3O+]
- [H3O+] =10−Ph
- pH + pOH = 14
➢ pOH = − log [OH-]
➢ pH = 14 – pOH
- pKa = − log Ka
- pKb = − log Kb
- The weaker the acid (or base) the higher the value of pKa (or pKb )
- Ka Kb = Kw (AT ALL TEMPERATURES. AT EQUILIBRIUM)
- pKa + pKb = pKw = 14 (AT 25OC)
Anions can act as a BL base
- Anions that are conjugate bases of strong acids (eg Cl− ) are weak bases and they
have no effect on pH.
➢ NO3 − (aq) + H2O(l) → No Reaction
- Anions such as CO3− that are the conjugate bases of weak acids will raise the pH of a
solution.
➢ CO32−(aq) + H2O(l) → HCO3 − (aq) + OH− (aq)
- Alkali metal and alkaline earth cations have no measurable effect on solution pH.
➢ Na+(aq) + H2O(l) → No Reaction
• Since these cations are conjugate acids of strong bases, hydrolysis does not
occur.
- All metal cations are hydrated in water, forming ions such as [Metal(H2O)6 ]n+
NO EFFECT ON pH
Figure 2 REACTING A SALT IN WATER AND TAKING ITS IONS
Figure 5 IF THERE IS AN ACIDIC AND A BASIC ION, THE ONE WITH THE HIGHEST Ka/Kb value
dominates
𝐾𝑤
𝐾𝑏 =
𝐾𝑎
➢ To find where equilibrium lies in Acid-base reactions: Compare Ka and Kb
values of each reactants and each products and the side with the lowest Ka and
Kb value is favoured because it has the weak base and acid
- Salt of weak base AND weak acid: Kb > Ka Basic (eg, NH4CN)
➢ Weak base + Weak acid -> Basic salt
➢ NH3 + HCN -> NH4CN
• NH4CN -> NH4+ + CN-
✓ NH4+ -> Cation of a weak base -> Will release H+ INTO solutions->
ACIDIC
✓ CN- -> Anion of Weak acid (HCN) -> Will INCREASE pH (Will react with
H2O and take away H+ from solutions) -> BASIC
✓ BUT BECAUSE kb>Ka, the base (CN-) will dominate and the solution
will be basic
- Salt of weak base AND weak acid: Kb < Ka Acidic (eg, NH4F)
➢ Weak base + weak acid -> Acidic salt
➢ NH3 + HF -> NH4F
• NH4F -> NH4+ + F-
✓ NH4+ -> Cation of a weak base -> Will release H+ INTO solutions->
ACIDIC
✓ F- -> Anion of Weak acid (HF) -> Will INCREASE pH (Will react with H2O
and take away H+ from solutions) -> BASIC
✓ BUT BECAUSE kb<Ka, the acid (NH4+) will dominate and the solution
will be acidic
- All proton transfer reactions proceed from the stronger acid and base to the weaker
acid and base.
- When a weak acid is in solution, the products are a stronger conjugate acid and base.
Therefore equilibrium lies to the left.
➢ The reaction favours the side having the weaker acid and base
OXYACIDS
a. The more (electronegative) oxygen atoms get attached to the central atom on the
base (A-)…
➢ If more EN atoms are attached to the central atom of the acid (A), then the base
(A-) can better stabilise the charge -> Stronger acid-> eq right/Forward
b. There is a possibility of resonance on the base (A-), to delocalise the charge …
➢ Possibility of resonance than more stable -> Equilibrium lies to the right
c. … greater positive formal change on central atom in base (A-)…
➢ Leads to greater stabilizations
- For stronger acids the base can better accommodate and stabilise the additional
negative charge.
➢ If the base (A-) can accommodate the negative charge (If a base forms in such a
way that the electron density can be stabilised then the base is a better base and
equilibrium lies to the right) then the acid will be stronger.
ANIONS AS BASES
- The high the negative charge = The more basic the oxoanion = Pulls H+ towards itself
- OXOANIONS: eg) PO43- , HPO42- , H2PO42- , H2PO4- , CO32- , HCO3- , SO32- , HSO3-
Figure 6 Ka and Kb values
LEWIS ACIDS AND BASES
[𝐶𝑜𝑛𝑗 𝑏𝑎𝑠𝑒]
𝐻3 𝑂+ = × 𝐾𝑎
[𝐴𝑐𝑖𝑑]
[𝐶𝑜𝑛𝑗 𝑏𝑎𝑠𝑒]
➢ If = 1 then pH = pKa
[𝐴𝑐𝑖𝑑]
[𝐶𝑜𝑛𝑗 𝑏𝑎𝑠𝑒]
➢ If > 1 then pH > pKa
[𝐴𝑐𝑖𝑑]
[𝐶𝑜𝑛𝑗 𝑏𝑎𝑠𝑒]
➢ If < 1 then pH < pKa
[𝐴𝑐𝑖𝑑]
ALSO
- Eg) Calculate the mass of NH4Cℓ that must be used to prepare 500. mL of a buffer
solution that is 0.10 M in aqueous NH3 and has a pH of 9.15, Kb (NH3 ) = 1.8 x 10-5.
(WHEN ASKED TO CALCULATE THE MASS OF A SALT USED TO PREPARE A CERTAIN
VOLUME OF A BUFFER WITH NOWN CONCENTRATION AND pH )
1. When given a salt and asked to calculate its pH dissociate the salt and take the
non-neutral ion and match it with its acid or base and react it.
2. Find pH or pOH and use it to find H+ or OH- Concentration
3. Use Kb or Ka to find the required Concentration (in this example we would find
NH3 concentration)
4. Use n=C/V to find mass
- Calculating pH when the products are not 0
1. Know that water can act as a weak base or acid but that its autoionization will have
no effect on pH
2. Know that the total volume will change upon addition of water
3. Use ice table with the initial concentration being the given ones and use Ka to find
[H3O+] then find pH as normal
Buffer Capacity
- The amount (in moles) of H3O+ or OH ions that needs to be added to a buffer
solution to change the pH by 1 unit.
- pH range of buffer capacity: usable range
➢ Biggest range if [acid] = [base] → pH = pKa
- Usable range: pKa ± 1
TITRATIONS
- Equivalence point: moles of acid = moles of base
- Endpoint point: indicator changes color
- Goal: choose indicator whose endpoint is as close to the equivalence point as
possible
- A titrant is what is being added during a titration
- A titre is the initial solution
- At the halfway point: [HA] = [A-] ( [acid] = [Base] ) -> pH = pKa of HA
➢ The reaction mixture has a buffering effect and the pH change levels off
strong acid titrated with a strong base (acid in a flask and base added from a burette)
FINDING THE CONCENTRATIONS (of H3O+, OH-, conjugate of titre) AT EQUIVALENCE POINT.
a. write a balanced equation which has the conjugate of the titre
b. Calculate moles titrant using the steps above or it will be given
c. Total volume =Volume of titre + volume of titrant added
d. Concentration of the conjugate of the titre (use mole ratios between the titre
and its conjugate from the equation in a to find the concentration of the
conjugate using the titre’s concentration)
• Concentration of titre will be given or calculate it using the steps above
e. Use the Ice table, the initial concentration of the conjugate of the titre is the
concentration in number d and the concentration of the titre is 0 and
concentration of hydronium or OH- is also 0
f. Use Kb to find Ka if the Ka is not in the table-> Ka = Kw/Kb
g. Calculate equilibrium concentrations (of H3O+) using Ka expressions
h. Find [OH-] using [OH-] = Kw/[H30+] or
• Find pH using [H3O+]
• pH+pOH=14
• 10-pOH =[OH-]
• THE ONE IN RED IS THE SAFEST METHOD
i. Concentration of the conjugate of the titre = Initial concentration (number d) –
Equilibrium concentration (g)
• OR If we can make the approximation the initial concentration of the titre
conjugate = its initial concentration (number d)
FINDING pH AT THE EQUIVALENCE POINT
A. Find [H3O+]
B. pH= -log [H3O+]
INDICATORS
- pH range in which colour changes: pKa ± 1
- Choose an indicator with a pKa that’s close to the pH at the equivalence point
SOLUBILITY
- If Ksp >> 1 then Salt is considered to be soluble
- If Ksp << 1 then Salt is considered to be insoluble
- If Ksp 1 then Salt is slightly soluble
- Remember Common ION effect
- BALANCED EQUATION
- Use ICE table
R Solid salt Ion Ion
Initial
Change
Equilibrium
Determining if a precipitate will form
- Q = Ksp: The solution is saturated. Equilibrium position. Precipitate starts to form.
- Q < Ksp: The solution is not saturated/unsaturated: Can still add more.
- Q > Ksp: The solution is oversaturated, more precipitate forms.
CALCULATE Ksp GIVEN MASS OF ONE ION/OF SALT AND VOLUME OF SOLUTION
1. If mole ratio is 1:1 then the concentrations of the ions will be equal and their initial
concentrations are always 0 unless stated otherwise OR UNLESS THERE IS A
COMMON ION.
➢ If they tell us solution is saturated then all the salt dissolved.
3. Ksp = [Cation][Anion]
ESTIMATE SOLUBILITY OF SALT IN:
CHECKING IF A SALT WILL DISSOLVE AND HOW MUCH WILL DISSOLVE GIVEN ITS MASS AND
Ksp AND VOLUME OF WATER
1. Ksp= [cation][Anion]
2. Solve for X-> Solubility (in 𝑚𝑜𝑙/𝑙) -> THIS IS THE [SALT] IN SOLUTION
𝑚𝑜𝑙 𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 𝑠𝑎𝑙𝑡 (𝑔)
3. Convert to grams per liter ( × )
𝐿 1 𝑚𝑜𝑙
4. Get the mass that dissolved (𝐴𝑛𝑠𝑤𝑒𝑟 𝑓𝑟𝑜𝑚 𝑛𝑢𝑚𝑏𝑒𝑟 × 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑤𝑎𝑡𝑒𝑟)
5. Compare the answer in number 3 with the given mass if the mass in number 3< the
given mass then it did not all dissolve.
6. The dissolved mass is the one we got in number 3
COMPARE SOLUBILITY OF A SALT IN:
SOLUBILITY DECREASES IF THERE IS ALREADY A COMMON ION IN SOLUTION.
- PURE WATER
➢ Write full balanced reaction
➢ ICE TABLE WITH THE INITIAL ION CONCENTRATIONS BEING 0
➢ Solve for X
➢ Ksp = [Cation][Anion] -> SOLUBILITY WANTED
- WATER THAT HAS A CERTAIN CONCENTRATION OF A SALT WITH A COMMON ION
➢ The ion that already has a common ion wont have an initial concentration of 0 in
the solution.
➢ Perform same calculations as above
THEME 4: THERMODYNAMICS
Entropy: Level of disorder in a system. Number of microstates a system can have.
➢ Increase in energy of system = more microstates
➢ More molecules = More microstates
Second Law of Thermodynamics
High entropy
➢ High temp
➢ High volume
➢ Low pressure
• If for example the leften side has low number of “mole ratios” and the
righten side has high “mole ratios”: Entropy is high in the leften side but if
vice versa entropy is high.
➢ Large molecules
➢ Number of moles of gas increase (mole ratio)
➢ Heavy atoms
➢ Gas entropy> Liquid entropy>Solid
• If the reactants are liquids/solids and the products are gases: High entropy
but if vice versa then entropy is low
➢ Liquid entropy >Solid entropy
• If the reactants are liquids and the products are solids: low entropy but if
vice versa then entropy is high
• Eg) NH4Cl(aq) → NH4Cl(s)
• Eg) NaCl(s) → NaCl(l): High entropy
➢ Impure substances
∆𝑆𝑈𝑛𝑖𝑣𝑒𝑟𝑠𝑒 = 0 → 𝐸𝑞𝑢𝑖𝑙𝑖𝑏𝑟𝑖𝑢𝑚
∆𝑆𝑈𝑛𝑖𝑣𝑒𝑟𝑠𝑒 > 0 → 𝑆𝑝𝑜𝑛𝑡𝑎𝑛𝑒𝑜𝑢𝑠
∆𝑆𝑈𝑛𝑖𝑣𝑒𝑟𝑠𝑒 < 0 → 𝑁𝑜𝑛 − 𝑠𝑝𝑜𝑛𝑡𝑎𝑛𝑒𝑜𝑢𝑠
∆𝑆𝑈𝑛𝑖𝑣𝑒𝑟𝑠𝑒 = ∆𝑠𝑦𝑠𝑡𝑒𝑚 𝑆 + ∆𝑆𝑢𝑟𝑟𝑜𝑢𝑛𝑑𝑖𝑛𝑔𝑠 𝑆
∆𝑟 𝐻° (∑ 𝑛 𝐻°𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑠− ∑ 𝑛 𝐻°𝑅𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠 )
∆𝑆𝑢𝑟𝑟𝑜𝑢𝑛𝑑𝑖𝑛𝑔𝑠 𝑆 = −( ) = −( )
𝑇 𝑇
∆𝑟 𝐻° = ∑ 𝑛 𝐻°𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑠− ∑ 𝑛 𝐻°𝑅𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠
∆𝑟 𝐻°
𝑆𝑈𝑛𝑖𝑣𝑒𝑟𝑠𝑒 = ∆𝑠𝑦𝑠𝑡𝑒𝑚 𝑆 + −( )
𝑇
∆𝑟 𝐻 → ∆𝐻
𝑪𝑶𝑴𝑴𝑶𝑵 𝑸𝑼𝑬𝑺𝑻𝑰𝑶𝑵
ABOVE OR BELOW OR AT WHICH TEMP WILL reaction BE SPONTANEOUS?
1) ∆𝐺° = 0
2) 0 = ∆𝑟𝐻° − 𝑇∆𝑟𝑆°
∆𝑟𝐻°
3) 𝑇 =
∆𝑟𝑆°
4) Solve for T
5) Above T-> non spont
➢ below T-> Spont
➢ at T-> Equilibrium
∆𝑣𝑎𝑝𝐻
∆𝑠𝑦𝑠𝑡𝑒𝑚 𝑆 =
𝑇
∆𝑓𝑢𝑠𝐻
∆𝑠𝑦𝑠𝑡𝑒𝑚 𝑆 =
𝑇
∆𝑓𝑢𝑠𝐻 → 𝑁𝑒𝑔𝑎𝑡𝑖𝑣𝑒 𝑓𝑜𝑟 𝑓𝑟𝑒𝑒𝑧𝑖𝑛𝑔 𝑎𝑛𝑑 𝑐𝑜𝑛𝑑𝑒𝑛𝑠𝑎𝑡𝑖𝑜𝑛
∆𝑓𝑢𝑠𝐻
∆𝑠𝑦𝑠𝑡𝑒𝑚 𝑆 = −
𝑇
∆𝑟 𝐺 = ∆𝑟 𝐻 − 𝑇∆𝑟 𝑆
∆𝑟 𝐺° = ∆𝑟 𝐻° − 𝑇∆𝑟 𝑆°
∆𝑟𝐻° ∆𝑟𝑆° ∆𝑟𝐺° Rxn
Exo (-) ☺ Disorder (+) ☺ Spont (-) ☺ Product favoured
Endo (+) Order (-) Non spont (-)
Reactant
favoured
Exo (-) ☺ Order (-) Temperature
dependent
Endo (+) Disorder(+) ☺ Temperature
dependent
➢ ∆𝑟 𝐻° < 0 𝑎𝑛𝑑 ∆𝑟 𝑆° > 0: 𝐸𝑛𝑡ℎ𝑎𝑙𝑝𝑦 & 𝐸𝑛𝑡𝑟𝑜𝑝𝑦 𝑓𝑎𝑣𝑜𝑢𝑟𝑒𝑑
➢ ∆𝑟 𝐻° > 0 𝑎𝑛𝑑 ∆𝑟 𝑆° < 0: 𝑅𝑋𝑁 𝐹𝑎𝑣𝑜𝑢𝑟𝑠 𝑛𝑜𝑛𝑒
➢ ∆𝑟 𝐻° < 0 𝑎𝑛𝑑 ∆𝑟 𝑆° < 0: 𝐸𝑛𝑡ℎ𝑎𝑙𝑝𝑦 𝑓𝑎𝑣𝑜𝑢𝑟𝑒𝑑
➢ ∆𝑟 𝐻° > 0 𝑎𝑛𝑑 ∆𝑟 𝑆° > 0: 𝐸𝑛𝑡𝑟𝑜𝑝𝑦 𝑓𝑎𝑣𝑜𝑢𝑟𝑒𝑑
➢ ∆𝑟 𝑆° > 0: 𝐸𝑛𝑡𝑟𝑜𝑝𝑦 𝑓𝑎𝑣𝑜𝑢𝑟𝑒𝑑
➢ ∆𝑟 𝑆° < 0: 𝐸𝑛𝑡𝑟𝑜𝑝𝑦 𝑑𝑖𝑠𝑓𝑎𝑣𝑜𝑢𝑟𝑒𝑑
➢ ∆𝑟 𝐻° > 0: 𝐸𝑛𝑡ℎ𝑎𝑙𝑝𝑦 𝑑𝑖𝑠𝑓𝑎𝑣𝑜𝑢𝑟𝑒𝑑
➢ ∆𝑟 𝐻° < 0: 𝐸𝑛𝑡ℎ𝑎𝑙𝑝𝑦 𝑓𝑎𝑣𝑜𝑢𝑟𝑒𝑑
2) ∆𝑟 𝐻 = ∑ 𝑛 𝐻𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑠− ∑ 𝑛 𝐻𝑅𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠
∆𝑟 𝐺° = ∑ 𝑛 𝐺°𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑠− ∑ 𝑛 𝐺°𝑅𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠
→ 𝑎𝑡 25°𝑐, 1.0 𝑏𝑎𝑟, 1.0 𝑀(𝑆𝑡𝑎𝑛𝑑𝑎𝑟𝑑)
∆𝑟 𝐺 = ∆𝑟 𝐺° + 𝑅𝑇 𝑖𝑛(𝑄) → 𝐴𝑛𝑦 𝑡𝑒𝑚𝑝, 𝑛𝑜𝑡 𝑒𝑞, 𝑛𝑜𝑛 𝑠𝑡𝑎𝑛𝑑𝑎𝑟𝑑 𝑐𝑜𝑛𝑑𝑖𝑡𝑜𝑛𝑠
∆𝑟 𝐺° = −𝑅𝑇 𝑖𝑛(𝐾) → 𝐴𝑛𝑦 𝑡𝑒𝑚𝑝, 𝑎𝑡 𝑒𝑞
∆𝑟 𝐺 = ∆𝑟 𝐻 − 𝑇∆𝑟 𝑆 → 𝑎𝑛𝑦 𝑡𝑒𝑚𝑝, 1 𝑏𝑎𝑟, 1𝑀
𝑪𝑶𝑴𝑴𝑶𝑵 𝑸𝑼𝑬𝑺𝑻𝑰𝑶𝑵
Calculate equilibrium constant at a given temperature
1. ∆𝑟 𝑆°(𝑒𝑛𝑡𝑟𝑜𝑝𝑦 𝑜𝑓 𝑠𝑦𝑠𝑡𝑒𝑚/𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛) = ∑ 𝑛 𝑆°𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑠− ∑ 𝑛 𝑆°𝑅𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠
2. ∆𝑟 𝐻 = ∑ 𝑛 𝐻𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑠− ∑ 𝑛 𝐻𝑅𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠
3. ∆𝑟 𝐺° = −𝑇∆𝑟 𝑆°(𝑒𝑛𝑡𝑟𝑜𝑝𝑦 𝑜𝑓 𝑠𝑦𝑠𝑡𝑒𝑚/𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛) + ∆𝑟 𝐻°
4. ∆𝑟 𝐺° = −𝑅𝑇 𝑖𝑛(𝐾) → 𝐴𝑛𝑦 𝑡𝑒𝑚𝑝, 𝑎𝑡 𝑒𝑞
THEME 5: ELECTROCHEMISTRY
Oxidation Numbers
1. The oxidation number of a free element is always 0.
2. The oxidation number of a monatomic ion equals the charge of the ion.
3. The oxidation number of H is +1, but it is -1 in when combined with less electronegative
elements.
4. The oxidation number of O in compounds is usually -2, but it is -1 in peroxides.
5. The oxidation number of a Group 1 element in a compound is +1.
6. The oxidation number of a Group 2 element in a compound is +2.
7. The oxidation number of a Group 17 element in a binary compound is -1.
8. The sum of the oxidation numbers of all of the atoms in a neutral compound is 0.
9. The sum of the oxidation numbers in a polyatomic ion is equal to the charge of the ion.
BASIC TERMINOLOGY
CATHODE
ANODE
𝑪𝑶𝑴𝑴𝑶𝑵 𝑸𝑼𝑬𝑺𝑻𝑰𝑶𝑵𝑺
Calculate Eocell
THE MORE NEGATIVE EO BELONGS TO THE OXIDATION HALF CELL
1. Write Oxidation half reaction
2. Write reduction half reaction
3. Add the HALF REACTIONS and balance charges (ENSURE THE NUMBER OF
ELECTRONS CAN CANCEL OUT)
4. 𝐸°𝑐𝑒𝑙𝑙 = 𝐸°𝑟𝑒𝑑/𝑐𝑎𝑡ℎ𝑜𝑑𝑒 − 𝐸°𝑜𝑥/𝑎𝑛𝑜𝑑𝑒
➢𝑬 → 𝑪𝑬𝑳𝑳 𝑷𝑶𝑻𝑬𝑵𝑻𝑰𝑨𝑳
➢𝑬° → 𝑺𝑻𝑨𝑵𝑫𝑨𝑹𝑫 𝑪𝑬𝑳𝑳 𝑷𝑶𝑻𝑬𝑵𝑻𝑰𝑨𝑳
[𝑎𝑞𝑢𝑒𝑜𝑢𝑠 𝑝𝑟𝑜𝑑𝑢𝑐𝑡]
6. 𝑄 = [𝐴𝑞𝑢𝑒𝑜𝑢𝑠 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡]
➢ If we are using the standard hydrogen electrode then 𝐻 + 𝑎𝑛𝑑 𝐻2 are 1.0M
7. 𝑆𝑜𝑙𝑣𝑒 𝑓𝑜𝑟 𝑡ℎ𝑒 𝑚𝑖𝑠𝑠𝑖𝑛𝑔 𝑜𝑛𝑒
1 mol of the salt gives 1 mol of the ion when
it dissociates, sometimes it may not be a 1:1
ratio so you have to multiply.
CALCULATING K
𝑛𝐸°
➢ 𝐼𝑛(𝐾 ) = → 𝑎𝑡 25°𝑐 (IF THEY DON’T GIVE TEMPERATURE ASSUME
0.0257
25OC)
𝑛𝐹𝐸°
➢ 𝐼𝑛(𝐾 ) = → 𝑎𝑡 25°𝑐
𝑅𝑇
R= 8.314
ELECTROLYTIC CELLS
➢ Starts at source of electrical energy
➢ Electrical energy converted to chemical energy
➢ NON-SPONTANEOUS
➢ rG°> 0 (+) kJ, k<1
➢ E°<0 (-) Volt
➢ A battery is needed to “drive” the chemical reaction
QUESTION
Which product X or Y will most likely be at the anode in the electrolysis of an aqueous
solution of for example KF?
➢ Understand that Anode-> Oxidation
➢ Understand that aqueous solution contains water and water can also be reduced or
oxidized
➢ We have 2 possible Oxidation reactions. For X and For Y.
• X -> X ion +e
• Y -> Y ion + e
➢ We also have 2 possible reduction reactions, for ZK and for water. BUT KF is at the
very bottom of the redox table and cannot be reduced therefore water is the only
option that’s left for reduction
• 2H2O + 2e- -> H2 + 2OH-
➢ Calculate E cell for water and X and Eo cell for water and Y and compare them
➢ The combination that gives the smallest Eo cell (without considering the sign of the E
cell is preferred)
• Eg) If Water and X give an Eo cell of -2.3 and water and Y give an Eo cell of -3.5
we prefer the one for water and X because it requires the smallest potential (if
we don’t look at the sign) therefore X will be at the anode.
➢𝑮 ∘ = −𝒏𝑭𝑬°
➢𝑮 = 𝑮˚ + 𝑹𝑻 ln Q
➢𝐺 = −𝑛𝐹E
➢𝐸 = 𝐸° − 𝑖𝑛 (𝑄)𝑅𝑇
𝑛𝐹
→ 𝑁𝑜𝑛 𝑠𝑡𝑎𝑛𝑑𝑎𝑟𝑑 𝑐𝑜𝑛𝑑𝑖𝑡𝑖𝑜𝑛𝑠
➢𝑛(𝑚𝑜𝑙 𝑜𝑓 𝐸𝑙𝑒𝑐𝑡𝑟𝑜𝑛𝑠) → 𝑊ℎ𝑎𝑡 𝑑𝑖𝑑 𝑦𝑜𝑢 𝑚𝑢𝑙𝑡𝑖𝑝𝑙𝑦 𝑤𝑖𝑡ℎ 𝑡𝑜 𝑔𝑒𝑡 𝑏𝑎𝑙𝑎𝑛𝑐𝑒 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑛𝑠
➢If Q = 1, then 𝐸 = 𝐸˚
➢If Q > 1, then E <E˚
➢If Q < 1, then 𝐸 > 𝐸˚
𝟗𝟔𝟒𝟖𝟓 𝑪
𝟏 𝒎𝒐𝒍 𝒆−
QUESTION
Calculating the time taken to do electrolysis to get a certain mass of solid given the current.
➢ Find number of moles of solid to be formed
• Given mass * 1 mol/ Molar mass of solid to be formed
➢ Multiply the number of moles by mole ratio e-/ mole ratio solid
➢ Multiply the previous step by 96485 C/1 mol e-
➢ Use Q = It to solve for time
ORGANIC CHEMISTRY
THEME 1: STRUCTURE & BONDING
Single bond (−)-> Sigma bond (𝜎)
Double bond (=)-> 1 pie bond (𝜋) and 1 sigma bond(𝜎)
Triple bond (≡)-> Two pie bonds(𝜋) and 1 sigma bond(𝜎)
Number of hybrid orbitals/Type of orbital
➢ Number of lone pairs+ Number of sigma bonds
➢ If answer =3: Sp2
➢ If answer =2: sp
➢ If answer =4: sp3
Carbocation: 3 valence electrons. 3 bonds.
Carboanion: 5 valence electrons. 3 bonds and 1 lone pair.
Sp3 hybridization
➢ No unhybridized P orbitals, 4 sp3 orbitals
➢ Made by 3 P orbitals and 1 s
➢ Tetrahedral geometry
➢ Carbon: tetrahedral
➢ Nitrogen: Trigonal pyramidal
➢ Oxygen: bent
Sp2 hybridization
➢ 1 unhybridized P orbital (for pie bonds), 3 sp orbital (for sigma
bonds)-> 3 sp2 orbitals
➢ Made by 2 p orbitals and 1 s
➢ Trigonal planar geometry
➢ Carbon: trigonal planar
➢ Nitrogen: bent
➢ Oxygen: no shape
Sp hydridization
➢ 2 unhybridized P orbitals (for pie bonds), 1 sp (for sigma bonds
➢ Made by 1 p orbital and 1 s
➢ Linear geometry
➢ Carbon: linear
➢ Nitrogen: no shape
➢ Oxygen: no shape
BOLD line -> Forward
In plane -> Thin line
Behind -> dotted lines
➢ Name each orbital (1s,sp, sp3, sp2)
➢ Include approximate angles between 3 atoms
➢ Show type of bond
➢ Specify shape around non Hydrogen atoms
SKELETAL STRUCTURES
Minimum points
are for eclipsed
conformations
➢ Unstable
High energy
(electrons are
moving trying
- Torsional strain: Resistance to free rotation about C-C bonds due to the repel)
repulsion between bonding electron clouds
- Steric (van der Waals) strain arises when atoms or groups come closer than the sum
of their van der Waals’ radii
- Eclipsed conformations have both torsional and steric strains therefore they resist
rotation more.
NEWMAN PROJECTIONS
Front carbon
• Preferred trans (groups are not on the same side): Big group(s) on equatorial
- Compounds with the same molecular formula and the atom bonding pattern, but
different spatial arrangement of their atoms are called stereoisomers
• Eg) Cis and trans
Figure 7 ISOMER
Propyl-> Pr
Butyl-> Br
Methyl-> Methyl
Ethyl->Et
MeOH-> Methyl-OH
EtOH-> Ethyl OH
Nomenclature
SEPARATE NUMBERS BY COMMAS
SEPARATE LETTERS FROM NUMBER BY A HYPHEN
1. Find longest chain
2. Number carbons from the one near a branch/substituent or a group
3. Name substituents
- Di-> Two susbtituents
- Tri-> 3 substituents
- Tetra-> 4 substituents
4. Arrange substituents in alphabetical order and write complete name
- Ignore “tert” and “sec” when arranging in alphabetical order
NAMING CYCLOALKANES
1. Number carbons in the ring in such a way that the number for the groups are small
(eg, we prefer positions 2,3 instead of 5,6 -> so number carbons so that we get the
smallest positions for the substituents)
2. Then name alphabetically
3. IF THERE IS A LONGER CHAIN NOT PART OF THE RING, THE RING WILL BE A
SUBSTITUENT
- EG) Cyclobutyl,cyclopropyl, cyclomethyl
NEWMAN PROJECTIONS
- Show conformation about C-C bond
Prebuilt structure
- Yellow->Cl
- Blue-> Nitrogen/ Fluorine
- Green->Br
- Red-> OH
- White->H
- Black->Ethyl or Isobutyl
Staggered conformation: Much stable and has less energy because the electrons are far
apart
Eclipsed
➢ Less stable
➢ more energy because electrons are repelling
➢ Both torsional and steric strain present -> MORE RESISTANCE TO ROTATION
- Torsional strain: Resistance of rotation about the C-C bond due to the repelling
electrons
- Steric (van der waals) strain: Groups come closer than they should be
High energy-> ECLIPSED
Low energy->
STAGGERED
No torsional and
steric strain
THEME 3: STEREOCHEMISTRY
CHIRALITY
➢ Chiral molecules are mirror images of each other (non-superimposable)
➢ Lack plane of symmetry-> Cannot be cut in halves
➢ All 4 groups attached to the central carbon are different-> Therefore the carbon is a
chiral center
➢ Tetrahedral carbon makes the chiral center
- C=C: NOT TETRATHEDRAL
- C=O: NOT TETRAHEDRAL
- 𝐶 ≡ 𝐶: NOT TETRAHEDRAL
- THE ABOVE CANNOT BE CHIRAL CENTERS
Pair of enantiomers->
Chiral molecule and its
mirror image
➢ Divide rings in half from the atom of interest and if the halves are different the
carbon with the atom of interest is a chiral center
ACHIRAL
➢ Molecules that are superimposable
➢ Molecules that are identical
➢ Molecules with a plane of symmetry (you can cut the molecule in halves)
R,S SYSTEM/CONFIGURATIONS
1. Assign priority using atomic numbers
- LARGE ATOMIC NUMBER= HIGH PRIORITY (Number 1 to 4)
- Br (35)> Cl(17)> F(9)> O(8)> N(7)> C(6)> H(1)
2. Compare atoms directly attached to the chiral center first
- If the atoms are the same, compare the atoms attached to each of the same
carbons and put these atoms’ atomic numbers in square brackets (each square
bracket will have 3 atomic numbers)
- The one with the largest atomic numbers gets the next priority in line
• For multiple bonds-> Treat them as if it were more than 1 atom(eg, if we
have a double bond of Oxygen to carbon treat it as if the carbon has 2
oxygens)
3.
DRAWING ENANTIOMERS
1. Write the given molecule as a reflection without changing the wedged and dashed
bonds
OR
2. Change wedges to dashed bonds and dashed bonds to wedged bonds
STEREOISOMERS
50%R +50% S
2.HYDRATION
➢ Strong acid and High temperature
➢ OH goes to more substituted carbon
➢ H goes to less substituted carbon
• Regioselective
➢ Do not show stereochemistry
Mechanism for hydration (3 step)
➢ WHEN DRAWING LINE STRUCTURES FOR THE SUBSTRATES DO NOT DUPLICATE
THEM/DRAW SAME SUBSTRATE TWICE
3. HALOGENATION
- Antistereochemistry (show coming
and leaving bonds)
- Not regioselective
Mechanism for Halogenation
4. HALOHYDRIN FORMATION
- Antisterochemistry
- Regioselective
- X: Less substituted carbon
- OH: More substituted carbon
Mechanism for halohydrin formation
5. HYDROGENATION
- Syn stereochemistry (but the
hydrogens shouldn’t appear)
- Polar organic solvent use
(Ethanol)
- Heterogeneous (Has gas, liquid and solid phases)
- Aldehydes (COH), Ketone (COC), Carboxyls (COOR, COOH) survive hydrogenation
- Aromatic/benzene rings can undergo reactions at high pressure (136atm)
BENZENE STRUCTURE
- SHAPE
• Planar
• Perfect hexagon
• Bond angles are 120o
• Bond lengths are 139pm
• All carbons: sp2 hybridized
• All carbons: 3 sigma bonds
• All carbons: 1 p-orbital (1 pie bond)
- Nomenclature
• Benzene ring attached to a carbon chain: phenyl- substituent
•
THEME 5: SATURATED COMPOUNDS
NBS
In or
DMSO
NaOEt or
NaOR
NaOH
pyridine
NaOH
PCC OR
MeOH MeOH
Replace =O with OH
Zaitsev’s rule
➢ The major product is the one where there are more substituents around the C=C
bonds
REDUCTION
FORMATION OF ALKOXIDES
Substitution to alkyl HALIDES
Anti-stereochemistry Halogenation
Hydrohalogenation
n
REPLACE OH WITH A HALOGEN (Eg, Cl or Br) -> These are substitution reactions
THEME 6+7: CARBONYL COMPOUNDS
MONOSACCHARIDES
➢ Contain 3 – 7 carbons, formula CnH2nOn Possess a C=O group and all other
carbons are bonded to OH groups, except if specifically stated otherwise
➢ aldose = sugar with aldehyde FG
➢ ketose = sugar with ketone FG
• C3 = triose, C4 = tetrose, C5 = pentose, C6 = hexose
FISHER PROJECTIONS
➢ Fischer Projections are a standard way of representing the stereochemistry of sugars
- Vertical lines point into the page (away from you)
- Horizontal lines point out of the page (towards you)
- C’s at centre are omitted
- Monosaccharides are written with the carbon backbone vertical and the C=O
nearest the top
D and L sugars
D sugars: OH on second last carbon is to the right in the fisher projection
L sugars: OH on the second last carbon is to the left on the fisher projection
HAWORTH PROJECTION
➢ a flat ring with an O in the upper right position and substituents on vertical lines (–
up or down)
CH2OH up: OH on second last carbon is on the
OH up: On right in fisher projection. Therefore D sugar
the left in
Fisher
projection OH down: On the right in fisher
projection
➢ Both Fischer and Haworth projections are poor representations of the real shape of
monosaccharides.
➢ Six membered pyranose rings will adopt a chair conformation with the substituents
axial or equatorial
OXIDATION OF ALCOHOLS
EXCESS alcohol
HEMIACETALS
➢ Hemiacetals are the product when a hydroxyl group and a carbonyl group are part of
the same molecule and no other alcohol is present
- If another alcohol is present then the hemiacetal will be converted to the acetal.
ACETAL FORMATION IN SUGARS
- The acetal of a sugar is called a glycoside
- The bond to the external alcohol is called a glycoside bond
REDUCING SUGARS
➢ Aldoses are called “reducing” sugars because, in the process of being oxidised, they
reduce the oxidising agent
➢ Reducing sugars show mutarotation
➢ Hemi acetals are reducing sugars
➢ Reducing sugars have an OH on the carbon bonded to Oxygen.
ESTERS
Carboxylic + Alcohol -> Ester
Carboxylic + base -> Salt
HYDROLYSIS OF ESTERS
PEPTIDES
➢ The amide bond between two amino acids is called a peptide bond
REACTIONS OF AMIDES
NOMENCLATURE
➢ Stereoisomerism: Indicate whether double bonds are cis/trans or E/Z, and indicates
stereocentre (R, S).
➢ Substituents: Are groups coming off the main chain, including alkyl chains and other
functional groups. Halides & ethers are always substituents
➢ Parent: number of carbons in the main chain.
➢ Unsaturation: any double or triple bonds.
➢ Functional group: The most important functional group in the molecule (see data
sheet).
- PRIORITY: carbonyls > alcohols > thiols > amines > alkenes > alkynes > alkanes
STEPS
➢ Identify all the functional groups and choose the highest priority group to give the
suffix of the IUPAC name.
➢ Use the unsaturation block to indicate alkenes, alkynes or alkanes.
➢ The parent chain or ring must include as many functional groups as possible. The
longest carbon chain or ring with all the functional groups gives the parent name.
- For equal lengths choose to have as many side chains as possible .
➢ For rings, add “cyclo” to the start of the parent.
➢ All extra functional groups as well as ethers and halogens get named as substituents.
➢ Alkyl branches from the parent get named as substituents indicating the number of
carbons and the shape of the branch.
- Use di, tri, and tetra to indicate if there are 2, 3 or 4 of the same type of
substituent.
- List the substituents in alphabetical order according to the name of the
substituent
➢ After finding the parent and naming the substituents, choose the direction of
numbering.
➢ If there is a functional group, numbering is easy:
- number the chain from the end closest to the principal functional group OR
- number the ring with 1 at the C with the functional group, or no 1 and 2 for the
C’s of an alkene then proceed around the ring to give the next functional group
the smallest number.
- If there is no functional group revert to rules for branched alkanes: