General Chemistry C

Exam date & venue:

Nov. 16, 2024 (18:30-20:30)
良乡理教楼-202, 203
带计算器 Bring your calculator!
线下答疑时间：11月12日 9:30 ~ 13:30
11月15日 9:30 ~ 13:30
地点：工业生态楼922
Questions? Come to 922, Industrial Eco building
Nov. 12 9:30 ~ 13:30
Nov. 15 9:30 ~ 13:30
 Nomenclature

 Elements in the periodic table, allotropes

First 4 periods
 Simple binary compounds

 Significant Figures
 The 4th Period

3
by Kaycie D. http://kcd-elements.tumblr.com/
 smaller
Cation is always ___________ than
atom from which it is formed.

larger
Anion is always ___________ than
atom from which it is formed.
 Naming Inorganic Compounds
N2O5
• This is a molecular compound.
• The first element (N), just takes its name,
Nitrogen.
• The second compound takes its name, ending in
-ide, Oxide.
• Now we must consider how to show that there are
two nitrogen atoms, use di- as a prefix.
• Finally, we must consider how to show that there
are five oxygen atoms, use penta- as a prefix.
Dinitrogen Pentoxide
 How many Sig Figs?

1. 0.0004035 4
______
2. 100276 6
______
3. 2000 1
______
4. 150.40 5
______
5. 1.980 4
______

6
 To summarize

Use least accurate measurement when adding

and subtracting

Count sig figs when multiplying and dividing

7
 Structure of Matter

 Atomic structure (Proton, Neutron, Electron)

eg. 69Ga

 Electron configuration and periodicity

 Chemical bonds
 I、 Atomic structure

1. Atomic orbitals
wavefunction，ψ
can be expressed as ψn,l,m or symbols like 2px，3d
2. Four quantum numbers

degenerate orbitals
 II. Electron configuration

1. Rules for electron configurations

（1）Pauli’s Exclusion Principle
（2）The Lowest Energy Principle
（3）Hund’s rule
valence shell

These rules apply to ground state electrons.

Excited state electrons do not obey these rules.
2. Properties of Elements

Elements with low ionization energies lose electrons

easily to form cations.

Elements of B, Al, O and S show relatively smaller IE1

compared to their neighbors.
Hydrogen-like ions
Ionization energy ∝ Z2

13
III. Chemical bonding
1. Ionic bonds
2. Covalent bonds

(1) Direction, Saturation, Polarity

(2) Types of bonds: σ bonds, π bonds

3. Molecular orbitals
Second-Period Homonuclear Diatomic Molecules

第二周期同核双原子分子
1. The atomic number (Z) of Cr atoms is 24，so their
valence shell electron configuration is 3d44s2 ×
2. For the atom of the element with atomic number of 23,
[Ar] 3d 34s2
its electron configuration at ground state is __________，
the number of unpaired electrons is ________.
3
Thermodynamics

 Internal energy, U
 Enthalpy, H
 Entropy, S
 Gibbs energy, G
I. Internal energy, U
1. First law of thermodynamics
ΔU = Q + W
Constant p：ΔU = ΔH + W
2. U, Q and W
U is a state function
Q (heat) and W (work) are not state functions
Absorbing heat : Q > 0 Work done on the system: W > 0
Releasing heat: Q < 0 Work done by the system : W < 0

Volumetric work： Wvol= -pΔV

II. Enthalpy, H

Heat of reaction in an isobaric process, QP

1. At constant p, Qp = ΔH

2. H = U+pV

∆H > 0 endothermic；∆H < 0 exothermic

 3. Standard molar enthalpy of reaction, rHm

The heat change when the number of moles of reactants as

shown in the chemical equation reacts in standard conditions to
form products.

Stoichiometric number matters!

N2 (g)+ 3H2 (g)→2NH3(g) rHm= -92.22 kJꞏmol-1

1 3
N (g)+ 2 H2(g)→NH3(g) rHm= -46.11 kJꞏmol-1
2 2
Standard conditions in thermodynamics

Gas：T, p = p = 100kPa, ideal gas

Solution：T，p = p ，mass molar

concentration b = b = 1molꞏkg-1
Pure solid or liquid：T, p = p

No limitation on the value of T !

 4. Calculating rHmӨ

Using fHmӨ Standard molar enthalpy of formation

The enthalpy change of a chemical reaction where one mole

of a pure substance is formed from the free elements in their
most stable states (reference form) in standard conditions.

e.g. O2(g), H2(g), Br2(l), I2(s), C(graphite) and

P4(white phosphorus) are corresponding free elements in
their most stable states at 298K and pӨ.

ΔfHmӨ (reference form) = 0

 aA + bB → gG + dD
Standard conditions，298.15K：
Δr HmӨ  ν Δ H Ө B
B f m
B Ө
=[gΔf Hm (G)+dΔf Hm (D)]
Ө Ө
-[aΔf Hm (A)+bΔf Hm(B)]

Enthalpies of reactants and products both increase

with increasing temperatures

ΔrHmӨ (T) ≈ΔrHӨ

m (298.15K)
III. Entropy, S

1. Entropy（JꞏK-1）
State function，with absolute value，extensive

2. Third law of thermodynamics

The entropy of a pure, perfect crystalline substance (perfectly
ordered) is zero at absolute zero (0 K).
Standard molar entropy (SmӨ) can be calculated!
 3. Calculating ∆S

(1) Standard molar entropy change of reaction

rSmӨ = SmӨproducts - SmӨreactants

In chemical reactions,
 solid or liquid → gas, ΔS > 0
 If moles of gaseous species are more in products than
reactants, ΔS > 0
aA + bB → gG + dD 298.15K, standard conditions

 νB S m B 
Ө Ө
Δr Sm
B Ө Ө
=[g Sm (G) + dSm (D)]
Ө Ө
-[a Sm (A) + b Sm(B)]

Sm(reference form) ≠ 0!
At other T,
Ө Ө
ΔrSm (T) ≈ΔrSm (298.15K)
IV. Gibbs Energy, G
1. G = H-TS
State function，no absolute value，extensive
2. ∆G
ΔG =Wmax ′
3. The Gibbs energy change, ∆G, at constant T and p：
ΔG < 0 Spontaneous
ΔG > 0 Non-spontaneous
ΔG = 0 Equilibrium（e.g. chemical equilibrium，
phase transition)
Phase transition is reversible!
4. Calculating ∆G
ΔG =ΔH- TΔS

Ө
Ө
Ө
(A) ΔG in standard conditions at 298K
aA + bB → gG + dD
Δr Gm Ө  νBΔ f G mӨ(B)
B
=[gΔf Gm (G)+dΔf GmӨ (D)]
-[aΔf GmӨ (A)+bΔf GmӨ(B)]

Ө Ө
ΔrGm(298K) = -zFEcell (298K)
(B) Standard conditions, not 298K
ΔrGmӨ (T) = ΔrHmӨ(T)-TΔrSmӨ (T)

≈ΔrHmӨ(298.15K)-TΔrSmӨ (298.15K)

Can be calculated from ΔfHmӨ and SmӨ

Ө Ө
ΔrGm(T) = -RTlnK (T)
(C) Any conditions，any T

ΔrGm(T) =ΔrGm(T) + 2.303RTlgΠB

298 K and any conditions, ΔrGm= -zFE

1. For a certain reaction, if rH>rG, then rS >0. √

2. For reaction CH4(g)+2O2(g)→CO2(g)+2H2O(l) rS=0

×
3. A mixture must be a multi-phase system and a pure
substance must be single-phased. ×

4. For a certain reaction, if rG Ө <0, then the reaction

must be spontaneous at any condition.
×
5. If fHӨm (Ag2O, s) = a kJꞏmol-1, then for the reaction
of 2 Ag2O(s) → 4Ag(s) + O2(g), ΔHmӨ = -2a kJꞏmol-1
Chemical equilibrium

 Acid-base equilibrium
 Coordination equilibrium
 Redox equilibrium
I. Chemical equilibrium
1. Standard equilibrium constant
aA(g) + bB(aq) cC(s) + dD(g) +hH(l)
d
[ p(D)/p ]
K  a b
[ p(A) / p ] [b(B) / b ]

pB = ptotal nB = ptotal . xB
n
 2. The meaning of standard equilibrium constant
(1) lgK = -rGm(T)/2.303RT

Standard equilibrium constants are only functions of temperature

Coordination equilibrium: KfӨ

Redox equilibrium:
 (2) For multiple equilibria

If Reaction1→Reaction2 + Reaction3 Kϴ1=Kϴ2.K3ϴ

If Reaction1→Reaction2 - Reaction3 K ϴ1=K ϴ2/K3ϴ

Standard equilibrium constants of forward reaction and

reverse reaction are inversely proportional.
 3. Applications of standard equilibrium constants
(1) Estimating the tendency of the reaction
lgK = -rGm (T)/2.303RT
The higher the KӨ, the higher the tendency that the reaction forwards

(2) Predicting the direction of the reaction

ΔrGm(T) = 2.303RTlgΠB/K

When ΠB<Kϴ ΔrGm < 0 move forward

When ΠB=Kϴ ΔrGm = 0 at equilibrium
When ΠB>Kϴ ΔrGm > 0 move backward
1、NO(g) + CO(g) = 1/2N2(g) + CO2(g)，
rH(298.15 K)= -374 kJmol-1 .
To reduce the conversion percentage, one needs
(A) low temperature high pressure
(B) high temperature high pressure
(C) low temperature low pressure
(D)
√ high temperature low pressure
II. Coordination equilibrium
Cu2++4NH3 == [Cu(NH3)4]2+
2 ϴ
ϴ b([Cu(NH 3 ) 4 ] )/b
Kf ([Cu(NH3)4 ]2+)  2 ϴ ϴ 4
{b(Cu )/b }  {b(NH 3 )/b }

Transition between coordination equilibria

[Ag(NH3)2]+ + 2CN- → [AgCN2]– + 2NH3

Calculate the new standard equilibrium constant to

estimate if the reaction tends to move forward
1. For [Cu(NH3)4]2++Zn2+→ [Zn(NH3)4]2+ +Cu2+，if
Kfϴ([Cu(NH3)4]2+) > > Kfϴ([Zn(NH3)4]2+ )， the reaction
cannot actually proceed forward under standard
conditions. √
 III. Redox equilibrium
1. Galvanic cell
Components (Electrodes, salt bridge, external circuit)

2. Half-cell reaction and cell reaction

Negative electrode (anode)，oxidation

Zn2+(aq)+2e- Zn(s)
Positive electrode (cathode)，reduction

2H+(aq)+2e- H2(g)
Redox reaction
Zn(s)+2H+(aq) Zn2+(aq)+H2(g)
3. Standard electrode potential

T= 298.15K，all substances in standard conditions

Reflecting the tendency of losing/gaining electrons, not

dependent on stochiometric numbers

4. Nernst equation
0.0592V b(O) / b
E (O/R)  E (O/R)  lg
z b(R) / b

MnO4- + 8H+ + 5e- → Mn2+ + 4H2O

2H+ + 2e- → H2（g）
Hg2Cl2 (s) + 2e- → 2Hg(l) + 2Cl-
 I．Effect of concentrations on E
II．Effect of acidity on E
III．Effect of forming coordination complexes on E
IV．Effect of forming precipitates on E

Find the cell reaction and write the Nernst equation

E(O/R) ↑
the strength of oxidizing agent increases and the strength of reducing
agent decreases

E(O/R) ↓
the strength of reducing agent increases and the strength of oxidizing
agent decreases
V. Applications of electrode potential

(1) Calculating Electromotive force, emf

Std. conditions: Ecell = Ecathode - Eanode

Other conditions: Ecell = Ecathode - Eanode

(2) Predict the direction of reaction

Any state: rGm(T)= -zFEcell

E > 0 ΔG < 0 Forward reaction is spontaneous

E = 0 ΔG = 0 The reaction is at equilibrium
E < 0 ΔG > 0 Reverse reaction is spontaneous
(3) Estimating the strength of oxidizing and reducing agents

 A very positive E(Ox/Red) suggests the oxidized species in the redox couple
is strongly oxidizing and the reduced species is weakly reducing

 A very negative E(Ox/Red) suggests the oxidized species in the redox couple
is weakly oxidizing and the reduced species is strongly reducing

(4) Calculate K for electrochemical reactions

1. For two galvanic cells with cell reactions of √
Pb2+(aq) + 2e-→ Pb(s) and
0.5 Pb2+(aq) + e-→ 0.5 Pb(s)
if [Pb2+] = 1 molkg-1 , they have same electromotive force.

2. Atomic orbitals with the same principal quantum number

may not have the same energy. √

3. The electron configuration for valence shell of Cu atoms

is 4s1。 ×
4. If E Ө(Fe2+/Fe) = -0.45V，E Ө(I2/I-) = 0.54 V，
E Ө(Fe3+ /Fe2+) = 0.77 V, E Ө(Br2/Br-) = 1.07 V，
E Ө(Cl2/Cl-) =1.36 V，EӨ(MnO4-/Mn2+) = 1.51 V,
Then under standard conditions，
(1). The most strong reducing agent is ______,
Fe the
-
MnO
most strong oxidizing agent is ______________。
4

Fe3+
(2). Choosing ___________ as the oxidizing agent
can only oxidize I- but not Br-.
5. Upon thermal decomposition,
2Ag2O(s)→4Ag(s)+O2 (g)
At 298K, fHm Ө (Ag2O,s) = -31.1 kJmol-1，
fGmӨ(Ag2O,s) =-11.2 kJmol-1
(1) Please calculate rSmӨ (298.15 K)
(2) At 298K，please calculate KӨ.
(3) At 298K，please calculate p(O2) at equilibrium.
(4) Calculate the thermal decomposition T of Ag2O(s).
(5) At 500K, please calculate KӨ
(6) At 298K, if p(O2)=10kPa, the reaction will go
forward or backward?
6. For Fe2+ (aq) +Ag+ (aq) = Fe3+ (aq) + Ag (s),
if [Fe3+] = [Fe2+] ，
（1）What is [Ag+] when the electromotive force is
zero for a battery with this cell reaction?
（2）At 298K，please calculate KӨ and ΔrGmӨ
（3）At 298 K, when b(Ag+) = 0.1molꞏkg-1, please
calculate ΔrGm=？
EӨ(Fe3+/Fe2+)=0.771V, EӨ(Ag+/Ag)=0.799V