Boiling Point, and Melting Point

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General Chemistry 2 Review (Lessons 1-4)

Lesson 1: Intermolecular Forces of Liquids and Solids

Learning Outcomes:
• Describe and differentiate the types of Intermolecular Forces (IMFs)
• Predict the IMFs possible for a molecule
• Explain the effects of IMFs on these properties: surface tension, viscosity, vapor pressure,
boiling point, and melting point
(Note: Heating curves, Types of Solids, and Phase Diagram are not included in the exam.)

Important points to remember:


• Intermolecular forces (IMFs) are nonbonding forces that hold molecules together. IMFs are
much weaker than bonding (intramolecular) forces. There are 4 general types of IMFs namely
(in order of increasing strength):
Dispersion (London)
Dipole-dipole
Hydrogen bond
Ion-dipole
• Dispersion (London) forces are instantaneous dipole-induced dipole forces that occur among
all particles and increase with number of electrons (molar mass). For nonpolar molecules, only
dispersion force is present.
• Dipole-dipole forces occur between oppositely charged poles or polar molecules.
• Hydrogen bonding, a special type of dipole-dipole force, occurs when H bonded to N, O, or F is
attracted to the lone pair of N, O, or F in another molecule.
• Ion-dipole forces occur between ions (ionic compounds) and polar molecules.
• IMFs affect physical properties like surface tension, viscosity, vapor pressure, boiling point,
and melting point. In general, when strength of IMFs increases, surface tension increases,
viscosity increases, vapor pressure decreases, and boiling point and melting point increase.
For boiling point, the larger the molar mass and surface area, the higher the boiling point.

Problems
Identify the dominant type of IMF present in the following substances.
1. CBr4 It is nonpolar so the only IMF present is Dispersion force.

2. CaF2 (aq) CaF2 is an ionic compound. Notice that there is a symbol (aq) beside it
which means that it is dissolved in water. An ionic compound + water has
Ion-dipole force.

3. NCl3 NCl3 is a polar molecule because its shape is trigonal pyramidal. There is
no H bonded to N, O, or F, so the IMF is Dipole-dipole.

4. H2 It is nonpolar so the only IMF present is Dispersion force.

5. Ar It is nonpolar so the only IMF present is Dispersion force.

6. KBr + H2O KBr is an ionic compound which is mixed with water. An ionic compound +
water has Ion-dipole force.

7. CH3OH CH3OH is a polar molecule. H is bonded to O which means that it has a H-


bonding.

8. CH3CH2CH3 CH3CH2CH3 is a hydrocarbon is it is a nonpolar molecule. It only has


Dispersion force.

9. CH3OCH3 CH3OCH3 is a polar molecule with a bent shape. The Hs here are
connected to C only so there is no H-bonding. The IMF is Dipole-dipole.

10. NH3 NH3 is a polar molecule because its shape is trigonal pyramidal. H is
bonded to N here, so the IMF is H-bonding.
From the 2 substances given, underline the one that correctly applies the description and briefly
justify your answer.

1. greater pressure [H2O, H2] – H2 has greater pressure because its IMF is dispersion. H2O has H-
bonding. Dispersion is weaker than H-bonding. The weaker the IMF of the substance, the faster it is
to form vapor pressure.

2. higher boiling point [CH4, C2H6] – both have dispersion forces because they are nonpolar
molecules but C2H6 has higher boiling point because its molar mass is greater.

O
C
3. stronger surface tension [CH3OH, H H ] – both are polar molecules; CH3OH has H-bonding
while the second molecule has dipole-dipole force. The stronger the IMF, the stronger the surface
tension. CH3OH has stronger surface tension because H bonding is stronger than dipole-dipole.

4. more viscous [rubbing alcohol, honey] – The stronger the IMF, the more viscous the substance.
Honey is more viscous than alcohol because honey has many H bondings while rubbing alcohol has
only one.

Lesson 2: Solutions and their Properties

Learning Outcomes:
• Describe the different types of solutions
• Express concentrations of solutions in terms of mass %, molarity, molality, mole fraction, and
parts per million
• Differentiate the colligative properties of nonelectrolyte and electrolyte solutions
(Note: Colligative properties calculations -- vapor pressure lowering, freezing point depression,
boiling point elevation, and osmotic pressure -- are not included in the exam)

Important points to remember:


• A solution is a homogeneous mixture of a solute dissolved in a solvent through the action of
intermolecular forces.
• If similar intermolecular forces occur in solute and solvent, they replace each other when the
substances mix and a solution is likely to form (like dissolves like)
• Solutions can be solid, liquid, or gas. In terms of the amount of solute present, solutions can be
classified as unsaturated, saturated, or supersaturated.
• The concentration of a solution is independent of the quantity of solution and can be expressed
as % by mass (w/w), % by volume (v/v), % by mass-volume (w/v), molarity, molality, mole
fraction, or parts per million (ppm).

% by mass:

% by volume:

% by mass- volume:

Molarity:

Molality:
Mole fraction:

Parts per million:


Also expessed as

• Colligative properties arise from the number, not the type, of solute particles.
• Compared to pure solvent, a solution has lower vapor pressure (Raoult’s Law), elevated boiling point,
and depressed freezing point, and it gives rise to osmotic pressure

P pure solvent > P solution


Tb pure solvent < Tb solution
Tf pure solvent > Tf solution

• Calculating colligative properties of electrolyte solutions requires a factor (i), called van’t Hoff factor,
that adjusts for the number of ions per formula unit.
For covalent compounds/nonelectrolytes, i = 1
For ionic compounds/electrolytes, i depends on the number of ions present
For example, sucrose (C12H22O11) is a covalent compound/nonelectrolyte, i =1
magnesium chloride (MgCl2) is an ionic compound/electrolyte, i = 3 because there are 3
ions present – 1 Mg2+ and 2 Cl-

Problems
1. What is the molarity of an 85.0 mL ethanol (C2H5OH) solution containing 1.77 g of ethanol?
(MC2H5OH = 46.08 g/mol)

Given: V = 85.0 mL C2H5OH solution


mC2H5OH = 1.77 g
Required: M
Solution:
Where mole solute = 1.77 g C2H5OH x 1 mol = 0.0384 mol
46.08 g

V solution = 85.0 mL x 1 L = 0.0850 L


1000 mL
M = 0.0384 mol
0.0850 L
M = 0.451 mol/L or 0.451 M

2. How many grams of potassium dichromate (K2Cr2O7) are required to prepare a 250. mL solution
whose concentration is 2.16 M? (MK2Cr2O7 = 294.20 g/mol)

Given: V = 250. mL K2Cr2O7 solution = 0.250 L


M = 2.16 mol/L
Required: mK2Cr2O7
Solution:

Since mass is related to mole, derive the formula first to find moles:

Mole solute = M x Volume solution


= 2.16 mol x 0.250 L
L
= 0.540 mol

mK2Cr2O7 = 0.540 mol x 294.20 g


1 mol
mK2Cr2O7 = 159 g
3. Determine the % by mass of a 1.66 g of C12H22O11 dissolved in 200. g of water.

Given: msolute = mC12H22O11 = 1.66 g


msolvent = mwater = 200. g

Required: % by mass
Solution:

= 1.66 g x 100
1.66 g + 200. g

% by mass = 0.823%

4. What is the molality of a solution prepared by dissolving 32.0 g of CaCl2 in 271 g of water? (MCaCl2
= 110.98 g/mol)

Given: msolute = mCaCl2 = 32.0 g


mwater = 271 g
Required: m

Solution:
Where mole solute = 32.0 g CaCl2 x 1 mol = 0.288 mol
110.98 g

mwater (in kg) = 271 g x 1 kg = 0.271 kg


1000 g
m = 0.288 mol
0.271 kg
m = 1.06 mol/kg or 1.06 m

5. A sample of rubbing alcohol contains 142 g of isopropyl alcohol (C 3H7OH) and 58.0 g of water.
What are the mole fractions of alcohol and water? (Misopropyl alcohol = 60.09 g/mol ; Mwater = 18.02
g/mol)

Given: mC3H7OH = 142 g


mwater = 58 g
Required: mole fractions of C3H7OH and water

Solution:

Where molC3H7OH = 142 g x 1 mol = 2.363 mol


60.09 g
molwater = 58.0 g x 1 mol = 3.219 mol
18.02 g

ΧC3H7OH = 2.363 mol


2.363 mol + 3.219 mol
ΧC3H7OH = 0.423

Χwater = 3.219 mol


2.363 mol + 3.219 mol
ΧC3H7OH = 0.577
Lesson 3: THERMOCHEMISTRY
Learning Outcomes:
• Explain the energy changes during chemical reactions
• Distinguish between exothermic and endothermic processes
• Explain the First Law of Thermodynamics
• Explain the enthalpy of a reaction
• Write the thermochemical equation for a chemical reaction

Important points to remember:


• Internal energy or simply energy (E) is transferred as heat (q) when system and surroundings
are at different temperatures or as work (w) when an object is moved by a force.
• Heat absorbed by a system (q > 0) or work done on a system (w > 0) increases the system’s
E; heat released by a system (q < 0) or work done by a system (w < 0) decreases its E. The
change in internal energy is the sum of the heat and work: ΔE = q + w. Heat and work are
measured in joules (J)
• Energy is always conserved; it can change from one form to another and move into or out of
the system, but the total quantity of energy in the universe (system + surroundings) is constant
• Enthalpy (H) is a state function, so any change in enthalpy (ΔH) is independent of how the
change occurred.
• ΔH equals qp, the heat released or absorbed during a chemical or physical change that takes
place at constant pressure.
• A change that releases heat is exothermic (ΔH < 0); a change that absorbs heat is
endothermic (ΔH > 0)
• We calculate ΔH of a process by calorimetry - measuring the energy transferred as heat at
constant pressure: q = mc ΔT , where m is mass of the substance, c is the specific heat
capacity of the substance, and ΔT is the difference between final temperature and initial
temperature.
• A thermochemical equation shows a balanced reaction and its ΔH value. The amount of a
substance (numerical coefficient in a balanced equation) and the quantity of heat are
thermochemically equivalent and act as conversion factors to find the quantity of heat
transferred when any amount of the substance reacts. An example of a thermochemical
equation is shown below:
Decomposition of water to its elements
H2O(l) → 2H2(g) + O2(g) ∆H = 572 kJ/mol
• The standard enthalpy of reaction (ΔH0rxn) is the enthalpy of a reaction carried out at 1 atm:
Horxn =  n (Hof) products -  n (Hof) reactants

Problems
1. A system receives 875 J of heat and delivers 540 J of work. Calculate the change in the internal
energy, E, of the system.

Plan: Define system and surroundings, assign signs to q and w and calculate ΔE. The verbs used in
the sentence describe the individual process as endothermic (+) or exothermic (-).

Solution: ΔE = q + w where q = 875 J ; w = -540 J


= 875 J + (-540 J)
ΔE = 335 J

3. Calculate q when 28.6 g of water is heated from 22.0C to 78.3C. The specific heat capacity of
water is 4.184 J/g·oC

Given: m = 28.6 g c = 4.184 J/ g·oC Tf = 78.3oC Ti = 22.0oC


Required: q
Solution: q = mcΔT
= (28.6 g) (4.184 J/g·oC) (78.3oC – 22.0oC)
q = 6740 J
4. An unknown mass of heated iron (initially at 500.0⁰C) was quickly transferred to a calorimeter
containing 240. g of water (initially at 20.0oC). When thermal equilibrium is reached, the system has a
temperature of 42.0oC. Calculate the mass of the iron. c of iron = 0.451 J/g oC and c of water = 4.184
J/g·oC

Given: Tiiron = 500.0oC Tiwater = 20.0oC


Tfiron = 42.0o Tfwater = 42.0oC
miron = ? mwater = 28.6 g
ciron = 0.451 J/ g·oC cwater = 4.184 J/g·oC
Required: miron
Solution: q = mcΔT
qsys = – qsurr

mironcironΔTiron = – mwatercwaterΔTwater
miron = – mwatercwaterΔTwater
cironΔTiron
= – (28.6 g) (4.184 J/g·oC) (42.0oC – 20.0oC)
(0.451 J/ g·oC) (42.0oC – 500.0oC)
miron = 12.7 g

5. Calculate the Hrxn from Hf for the following reaction: H3AsO4(aq) + 4H2(g) → AsH3(g) + 4H2O(l)

Hf [H3AsO4(aq)] = -904.6 kJ/mol


Hf [H2(g)] = 0 kJ/mol
Hf [AsH3(g)] = 66.4 kJ/mol
Hf [H2O(l)] = -285.8 kJ/mol)

Solution:
Horxn =  n (Hof) products -  n (Hof) reactants
= [1 mol (66.4 kJ/mol) + 4 mol (-285.8 kJ/mol)] – [1 mol (-904.6 kJ/mol) + 4 mol (0 kJ/mol)
= -1076.8 kJ – (-904.6 kJ)
Horxn = -172.2 kJ

Lesson 4: Chemical Kinetics

Learning Outcomes:
• Describe how various factors influence the rate of a reaction
• Write the mathematical relationship between the rate of a reaction and concentrations of the
reactants

Important points to remember:


• Chemical kinetics focuses on reaction rate, the change in concentration over time.
• Under a given set of conditions, each reaction has its own rate.
• The factors that influence occurrence of reaction and reaction rate are: reactant concentration,
reactant particle collisions, activation energy, presence of catalysts, and reaction temperature
• Concentration affects rate by influencing the frequency of collisions between reactant
molecules.
• Temperature affects rate by influencing the frequency and, more importantly, the energy
(activation energy) of the collisions between reactant molecules.
• The expression for a reaction rate and its numerical value depend on which reaction
component is being referenced.
• For any reaction, aA + bB → cC + dD, where a, b, c, and d are coefficients of the balanced
equation, the rate expressions are as follows:
1 A
RateA = - a t
(the rate of disappearance of substance A)
1 B
RateB = - b t
(the rate of disappearance of substance B)

1 C
RateC = + (the rate of appearance/formation of substance C)
c t

1 D
RateD = + (the rate of appearance/formation of substance D)
d t

• The negative sign means that the concentration of the reactants decreases as the reaction
proceeds

Problems

1. Express the rate of the reaction below in terms of the formation of dinitrogen pentaoxide:
4NO2(g) + O2(g) → 2N2O5(g)
Answer:
1 N2O5
RateN2O5 =
2 t

2. Given the reaction: 4NO (g) + O2 (g) → 2N2O3 (g), how fast is [O2] decreasing when [NO] is
decreasing at a rate of 1.60x10-4 mol / L·s?
Answer:
[O2 1 [NO
Rate = - = - 4 t
t

[O2 1 [NO
- = - t
4
t
substitute the given rate of [NO] as a negative value (-1.60x10-4 mol / L·s) into the expression
[O2 1
- = - 4
(-1.60x10-4 mol / L·s )
t

[O2
- t
= 4.00x10-5 mol / L·s

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