CHEMISTRY

“INTERMOLECULAR FORCES AND LIQUIDS AND SOLIDS”

KINETIC MOLECULAR MODEL OF LIQUIDS AND SOLIDS

- Solid particles have the least amount of energy, and gas particles have the greatest amount of
energy.
- Phase changes when energy of particles change

Kinetic molecular theory- Large number of small particles(atoms or molecules), all of which are in
constant, random motion

Lattice – Regular spacing/arrangement of atoms/molecules within a crystal.

Phase – Distinguished by chemical composition and/or physical state. (solid, liquid, or gaseous
phases)

An application of the theory is that it helps to explain why matter exists in different phases (solid,
liquid, and gas)

- Energy varies in its temperature

- Temperature of a substance- measurement of average kinetic energy

Diffusion – movement of particles from a high concentration to a lo concentration

INTERMOLECULAR FORCES

- Electrostatic interactions between molecules

There are three ways in which a water molecule move: (1) vibration, (2) rotation, and (3) translation.
Water molecules vibrate when H--O bonds are stretched or bent. Rotation involves the motion of a
molecule around its center of gravity. Translation literally means to change from one place to
another. It therefore describes the motion of molecules through space.

Intramolecular bonds

- The covalent bonds between the hydrogen and oxygen atoms in a water molecule (within)
- 25 times stronger that intermolecular
- Takes 464kJ/mol to break the H—O bonds within a water molecule

Intermolecular bonds

- the bonds between the neighboring water molecules in ice. (between)

- Only 19kJ/mol to break the bonds between water molecules.
- Strong intermolecular bonds- likely solid

Dipole-Dipole Forces

- The bonds in these molecules are said to be polar, because they have positive and negative
ends, or poles, and the molecules are often said to have a dipole moment.
 Ex. HCl molecules, for example, have a dipole moment because the hydrogen atom has a slight
positive charge and the chlorine atom has a slight negative charge. Because of the force of
attraction between oppositely charged particles, there is a small dipole-dipole force of attraction
between adjacent HCl molecules

Ion- Dipole

- An ion-dipole force is an attractive force that results from the electrostatic attraction between
an ion and a neutral molecule that has a dipole

Ex. An example of the ion-dipole interaction is the interaction between a Na + ion and water
(H2O) where the sodium ion and oxygen atom are attracted to each other, while the sodium and
hydrogen are repelled by each other
Dispersion forces

- or London dispersion force/ induced dipole-induced dipole attraction

- weakest intermolecular force.
- a temporary attractive force that results when the electrons in two adjacent atoms occupy
positions that make the atoms form temporary dipoles.
- If it is a covalent compound with non-polar bonds.

CHAPTER 5 THERMOCHEMISTRY

Energy- ability to do work or transfer heat

Thermodynamics- study of energy

Thermochemistry- the study of chemical reactions and energy changes involving heat

Heat- Energy used to cause the temperature to increase

Work- object that has mass to move (w=Fxd) from energy

ELECTROSTATIC POTENTIAL ENERGY

-THE MOST IMPORTANT FORM OF POTENTIAL ENERGY IN MOLECULES

Eel= KQ1Q2/d where k=8.99x109 J∙m/C2

Electron charge: 1.602x10-19C(Coulomb)

ATTRACTION BETWEEN IONS

Opposite charged ions- electrostatic attractions

energy released- chemical bonds formed

energy consumed- chemical bonds broken

FIRST LAW OF THERMODYNAMICS

1st Law- Energy cannot be created nor destroyed

SYSTEM AND SURROUNDINGS

System- molecules of interest (H2(g) and O2(g))

Surroundings- cylinder, piston, etc.

Open system- matter and energy can be exchanged with the surroundings.

Closed system- exchange energy- but not matter- w/ the surroundings.

Isolated system-neither both may be exchanged w/ the surroundings.

“Energy can enter or leave as heat/work done in piston”

“matter cannot enter or leave system”

INTERNAL ENERGY

- The sum of all kinetic and potential energies of all components of the system (E) ∆E= E final- Einitial
Einitial greater than Efinal, thus, energy is released from a system to surroundings during reaction and
∆E<0.

THERMODYNAMIC QUANTITIES: THREE PARTS

1) A number 2) a unit 3) a sign

- Positive ∆E results when the system gains energy from the surroundings.
- Negative ∆E results when the system loses energy to the surroundings.
ta

Sign conventions for q,w, and ∆E

For q + =system gains heat -= system loses heat
For w + = work done on system -=work done by system
For ∆E + = net gain of energy by -= net loss of energy by
system system

“When energy exchanged between the system & surroundings, it is either exchanged as heat(q) or work
(w). ∆E= q+w

Endothermic- heat is absorbed by the system from the surroundings

Exothermic- heat released by the system

STATE FUNCTIONS

“The internal energy of a system is independent of the path by which the system achieved that state.

“q and w are not state functions”

“q and w are different in two cases”

WORK

W= -P∆V

Where ∆V= Vfinal-Vinitial.

“Increase in volume means system does pressure- volume work”

Ex: Calculate the work(in J) associated with the expansion of a gas from 44mL to 63mL at a constant
pressure of 14atm

First we calculate
∆V= .063L- .044L= 0.019 L
Using P= 14 atm, we can then calculate
Work= -p ∙∆V = (14 atm) (0.019 L) = -0.266 atm-L
Using the conversion between atm-L and Joules of
1 L-atm = 101.325 J
Thus, we obtain
Work -0.0266atm – 101.325J 1kj = = -0.0027
L
1 atm-L 1000 J

ENTHALPY
Properties of Enthalpy
1.) Enthalpy is a state function
2.) Enthalpy is an extensive property
3.) Enthalpy is reversible
4.) ∆H for a reaction depends on the state of the products and the state of the reactants.
It is the thermodynamic function equal to the internal energy plus pressure x volume

H= E + PV

When the system changes at constant pressure, the change in enthalpy, ∆H, IS

∆H= ∆ ( E + PV); This can be written ∆H= ∆E +P∆V

Since ∆E = q +w and w = -P∆V, we can substitute these into the enthalpy expression:

∆H = ∆E + P∆V

∆H = (q + w) – w

∆H = q

The enthalpy change, ∆H, is defined as the heat gained or loat by the system under constant pressure.

∆H = qp.

ENDOTHERMIC AND EXOTHERMIC

 ∆H = Hfinal – Hinitial or ∆H = Hproducts – Hreactants

Endothermic = ∆H is positive (>0)

Exothermic = ∆H is negative (<0)

ENTHALPIES OF REACTION

∆H is called the enthalpy of reaction or the heat of reaction

A thermochemical equation is an equation for which ∆H is given:

2 H2 (g) + 02 (g) => 2 H2O(l) ∆H = -483.6 kJ

H2(g) + 1/2O2(g) => H2O(l) ∆H = -241.8 kJ

The enthalpy changes assume the coefficients are moles of the substances.

CALORIMETRY
- The measurement of heat released or absorbed by a chemical reaction
- The device used to measure heat
- The quantity of heat transferred by the reaction causes a change in temperature of the solution.
HEAT CAPACITY AND SPECIFIC HEAT
- The amount of energy required to raise the temperature of a substance by 1 K (1˚C) is its heat
capacity ( C in units of J/K). C= q/ ∆T
- The amount of energy required to raise the temperature of 1 g of a substance by 1 K.
- If the amount is 1 mole, it is the molar heat capacity.

CONSTANT PRESSURE CALORIMETRY

- Indirectly measure the heat change for the system
4.184 J/g ∙ K is well known specific heat for water, we can measure q for the reaction with this
equation
qsoln = Cs x m x ∆T = -qrxn

The calorimeter and its contents are the surroundings

qsoln is found from the mass, heat capacity, and temperature change

Ex: A metal pellet with mass 100.0 g, originally at 88.4˚C, is dropped into 125 g of water originally at
25.1˚C. The final temperature of both the pellet and the water is 31.3˚C.
Calculate the heat capacity C (in J/˚C) and specific heat capacity C S (in J/g.˚C) of the pellet. The
specific heat of water is 4.184 J/g. ˚C).

Bomb Calorimetry
- The volume in the bomb calorimeter is constant. What is measured is really the change in
internal energy, ∆E, not ∆H.
- The heat absorbed by the water is a very good approximation of the enthalpy change for the
reaction.
 - qrxn = Ccal x ∆T
HESS’S LAW

States that “If a reaction is carried out in a series of steps, ∆H for the overall reaction will be the
equal to the sum of the enthalpy changes for the individual steps”. ∆H is a state function

P= 1 atm (but for gases P = 1 bar)

T= usually 298.15 K (25.0˚C)

Concentration = 1mol/L

“WHEN 2 OR MORE THERMOCHEMICAL EQUATIONS ARE ADDED, THE ENTHALPY CHANGE OF THE
RESULATING EQUATION IS THE SUM OF THOSE FOR THE ADDED QUESTIONS”

Ex. Given the thermochemical equations

2WO2(s) + O2(g) => 2WO3(s) ∆H= -506kJ

2W(s) + 3O2(g) => 2WO3(s) ∆H= -1686 kJ

Calculate the enthalpy change for: 2W(s) + 2O 2(g) => 2WO2(s)

ENTHALPIES OF FORMATION

- The enthalpy changes for the reaction in which a compound is made from tis constituent
elements in their elemental forms.

STANDARD ENTHALPY OF INFORMATION

- The only one enthalpy value needed for each substance.

- The enthalpy changes when one mole of a substance in its standard state is formed from the
most stable form of the elements in their standard states.

STANDARD STATE

- Enthalpy changes depend on the temperature and pressure at which they are measured (When
applying Hess’s law, all values must refer to the same conditions of pressure and temperature)

STANDARD ENTHALPY OF FORMATION

- Symbol use is ∆Hf˚, where the ˚ designates standard state.

- “the product is always one mole of a single substance”
- The standard enthalpy of formation of the elements in their most stable form is ZERO

Ex.

C(graphite) + O2(g) => CO2(g) ∆Hf˚ [CO2(g)]

H2(g) + 1/2O2(g)=> H2O(l) ∆Hf˚[ H20(l) ]

2Na(s) + Se(s) + 2O2(g) => Na2SeO4(s) ∆Hf˚[ Na2SeO4(s) ]

 H2(g) => H2(g) ∆Hf˚[ H2(g) ] = 0

STUDY ENTHALPIES OF REACTION

BOND ENTHALPY

- The enthalpy associated with breaking one mole of a particular bond in a gaseous substance.
- Always positive because energy is required to break chemical bonds.
- Energy is released when a bond forms between gaseous fragments.
- The greater the bond enthalpy, the stronger the bond.

BOND ENTHALPIES AND ENTHALPIES OF REACTION

To obtain an estimate of ∆H,

- Add bond energy for all bonds made (+)

- Subtracts bond energy for all bonds broken (-)

∆Hrxn = ∑ (bond enthalpies - ∑ (bond enthalpies of bond bond broken) of bonds formed)

PRACTICE: PREDICT WHETHER A CHEMICAL REACTION WILL BE ENDOTHERMIC OR EXOTHERMIC USING

BOND ENTHALPIES)

ENERGY IN FOODS

Fuel value - The energy released when one gram of food is combusted

- Most of the energy in foods comes form carbohydrates, fat, and proteins

SEARCH HOW TO SOLVE

FUELS

- The vast majority of the energy consumed in this country.

CHAPTER 11 PROPERTIES OF SOLUTION

Molarity(M) = moles of solute / liters of solution
Mass(weight) percent = mass of solute / mass of solution x 100%
Mole fraction (�A) = molesA / total moles of solution
Molality (m) = moles of solute / kilogram of solvent

Molarity
Ex:
- You have 1.00 mol of sugar in 125.0 mL of solution. Calculate the concentration in units
of molarity. 8.00 M
 - You have a 10.0 M sugar solution. What volume of this solution do you need to have
2.00 mol of sugar? 0.200 L
- Consider separate solutions of NaOH and KCl made by dissolving 100.0 g of each solute
in 250.0 mL of solution. Calculate the concentration of each solution in units of molarity.
[100.0 g NaOH / 39.998 g/mol] / [250.0 / 1000] = 10.0 M NaOH
[100.0 g KCl / 74.55 g/mol] / [250.0 / 1000] = 5.37 M KCl
Mass Percent

What is the percent-by-mass concentration of glucose in a solution made my dissolving 5.5 g of glucose
in 78.2 g of water? [5.5 g / (5.5 g + 78.2 g)] × 100 = 6.6%

Mole fraction

A solution of phosphoric acid was made by dissolving 8.00 g of H3PO4in 100.0 mL of water.
Calculate the mole fraction of H3PO4. (Assume water has a density of 1.00 g/mL.)

8.00 g H3PO4× (1 mol / 97.994 g H3PO4) = 0.0816 mol H 3PO4

100.0 mL H2O × (1.00 g H2O / mL) × (1 mol / 18.016 g H2O) = 5.55 mol H2O

Mole Fraction (H3PO4) = 0.0816 mol H3PO4 / [0.0816 mol H3PO4 + 5.55 mol H2O] = 0.0145

Molality

A solution of phosphoric acid was made by dissolving 8.00 g of H3PO4in 100.0 mL of water.
Calculate the molality of the solution. (Assume water has a density of 1.00 g/mL.)

8.00 g H3PO4 × (1 mol / 97.994 g H3PO4) = 0.0816 mol H3PO4

100.0 mL H2O × (1.00 g H2O / mL) × (1 kg / 1000 g) = 0.1000 kg H2O

Molality = 0.0816 mol H3PO4/ 0.1000 kg H2O] = 0.816 m

COLLIGATIVE PROPERTIES
Raoult’s Law
Between 1887 and 1888, Francois-Marie Raoult showed that the vapor pressure of a
solution is equal to the mole fraction of the solvent times the vapor pressure of the pure liquid

P =Xsolvent (Po)

Po= Vapor pressure of solvent

P = Vapor pressure of the solvent in a solution

- When the solvent is pure, and the mole fraction of the solvent is equal to 1, P is equal
to Po
- Raoult's law suggests that the difference between the vapor pressure of the pure solvent
and the solution increases as the mole fraction of the solvent decreases.

Boiling Point Elevation and Freezing Point Depression

 - The decrease in the vapor pressure of the solvent that occurs when a solute is added to the
solvent causes an increase in the boiling point and decrease in the melting point of the solution.
- The equation that describes the magnitude of the boiling point elevation that occurs when
a solute is added to a solvent is therefore often written as follows.

∆TBP = kbm
- TBP - boiling point elevation
the change in the boiling point that occurs when a solute dissolve in the solvent.

kb – molal boiling point elevation constant for the solvent.

Ex.

Calculate the molecular weight of sulfur if 35.5 grams of sulfur dissolve in 100.0 grams of CS 2 to produce
a solution that has a boiling point of 49.48oC.

Solution

The relationship between the boiling point of the solution and the molecular weight of sulfur is not
immediately obvious. We therefore start by asking: What do we know about this problem?

We know the boiling point of the solution, so we might start by looking up the boiling point of the pure
solvent in order to calculate the change in the boiling point that occurs when the sulfur is dissolved in
CS2.

TBP = 49.48oC - 46.23oC = 3.25oC

We also know that the change in the boiling point is proportional to the molality of the solution.

TBP = kbm

Since we know the change in the boiling point (TBP) and the boiling point elevation constant for the
solvent (kb) can be looked up in a table, we might decide to calculate the molality of the solution at this
point.

m = TBP = 3.25oC = 1.38 m

kb 2.35oC/m

In the search for the solution to a problem, it is useful periodically to consider what we have achieved so
far. At this point, we know the molality of the solution and the mass of the solvent used to prepare the
solution. We can therefore calculate the number of moles of sulfur present in 100.0 grams of carbon
disulfide.

1.38 mol sulfur x 100.0 g CS2 = 0.138 mol sulfur

1000 g CS2
We now know the number of moles of sulfur in this solution and the mass of the sulfur. We can therefore
calculate the number of grams per mole of sulfur.

35.5 g = 257 g/mol

0.138 mol

The only way to explain this molecular weight is to assume that each sulfur molecule contains eight sulfur
atoms.

257 g/mol = 8
32 g/mol

Elemental sulfur therefore behaves as if it contains S 8 molecules.

Ex.2:

Eugenol, the active ingredient in cloves, has a formula, C 10H12O2. What is the boiling point of a solution
containing 0.154 g of this compound dissolved in 11.3 g of benzene? (Kbp = 2.53 °C m -1 and boiling
point of benzene = 80.1 °C)

Moles of eugenol = 0.154 g/164.2 g/mol = 9.38 × 10 -4 mol

Formula: Molality = no.of moles of solute / amount of solvent in kg
Molality = 9.38 × 10-4 mol/1.13 × 10-2 kg = 0.083m

Tbp = Kbp × m  Tbp = 2.53 °C m-1 × 0.083 m = 0.210 °C

Boiling point of solution = 80.1 °C + 0.210°C = 80.310 °C

TFP = -kfm (A negative sign is to indicate that the freezing point of the solvent decreases
when a solute is added.)

- TFP - freezing point depression

change in the freezing point that occurs when the solute dissolves in the solvent

- kf - molal freezing point depression constant for the solvent.

Ex:

Determine the molecular weight of acetic acid if a solution that contains 30.0 grams of acetic acid
per kilogram of water freezes at -0.93oC. Do these results agree with the assumption that acetic
acid has the formula CH3CO2H?
 Solution

The freezing point depression for this solution is equal to the difference between the freezing
point of the solution (-0.93oC) and the freezing point of pure water (0oC).

- TFP = -0.93oC - 0.0oC = -0.93oC

We now turn to the equation that defines the relationship between the freezing point depression
and the molality of the solution.

- TFP = - kfm

Since we know the change in the freezing point, and we can look up the freezing point depression
constant in a table, we have enough information to calculate the molality of the solution.

m = TFP = 0.93oC = 0.50 m

kf 1.853oC/m

- At this point, we might return to the statement of the problem, to see if we are making any
progress toward an answer. According to this calculation, there are 0.50 moles of acetic acid per
kilogram of water in this solution. The problem stated that there were 30.0 grams of acetic acid
per kilogram of water in the solution. Since we simultaneously know the number of grams and
the number of moles of acetic acid in this sample, we can calculate the molecular weight of acetic
acid.

30.0 g = 60 g/mol
0.50 mol

- The results of this experiment are in good agreement with the molecular weight (60.05 g/mol)
expected if the formula for acetic acid is CH3CO2H

Freezing Point Depression Constants

Compound Freezing Point (oC) kf (oC/m)

water 0 1.853
acetic acid 16.66 3.90
benzene 5.53 5.12
p-xylene 13.26 4.3
naphthalene 80.29 6.94
cyclohexane 6.54 20.0
carbon tetrachloride -22.95 29.8
camphor 178.75 37.7
 Boiling Point Elevation Constants

Boiling Point
Compound kb (oC/m)
(oC)
water 100 0.515
ethyl ether 34.55 1.824
carbon disulfide 46.23 2.35
benzene 80.10 2.53
carbon
76.75 4.48
tetrachloride
camphor 207.42 5.611

CHAPTER 16

Spontaneous- a reaction that will occur without intervention

-need both thermodynamics and kinetics to describe a reaction completely

Thermodynamics- compairs initial and final states

Kinetics- describes pathway between

THERMODYNAMICS

1st law- the enrgy of the universe is constant

Entropy- Disorder of randomness

-terms of probability

-most likely is the most random

2nd law- the entropy of the universe increases in any change

GASES

- Liquid have more ways for molecules to be arranged than solid but gases have more huge
number of positions possible

ENTROPY

2nd law- the entropy of the universe increases in any change

- GIBBS FREE ENERGY FORMULA

- Delta S univers= Total entropy change (TEC)
- If TEC is positive, the process is spontaneous
- If TEC is negative, the process is spontaneous in opposite direction
 - Tec DEPENDS ON TEMPERATURE

TEMPERATURE AND SPONTANEITY

-Entropy change in the surroundings and determined by the heat flow

- GIVING UP HEAT(exothermic process), the entropy of surroundings increases

-The size of TEC depends on temperature

GIBBS FREE ENERGY

-tells the spontaneity of a process (if it’s spontaneous or not)

D(delta)G= DH-TxDS

∆H- change in enthalpy

∆S- change in entropy

SPONTANEOUS IF -∆G

NONSPONTANEOUS IF +∆G( gibbs free energy)

(Spontaneous example on phone)

3rd law- The entropy of pure crystal at 0K is 0

- Standard entropies S ( at 298 K and 1 atm) of substances are listed

FREE ENERGY IN RECTIONS

∆G˚= standard free energy change

- Can’t be measured directly – calculated from other measurements

- ∆G˚=∆H˚-T∆S˚
- Use Hess’s Law with known reactions
- “SPONTANEITY tells nothing about rate”

STUDY FREE ENERGY and PRESSURE/ TEMPERATURE DEPENDENCE OF K/ FREE ENERGY AND WORK