Intermolecular Forces - Liquids and Solids Student Notes

Schematic Representations of the Three States of Matter

Gas Liquid Solid

Ion-Ion Interactions
The energy of ____________________ between two ions is proportional to the charges on the
ions and inversely proportional to the distance of separation.

q+ q-
F
d2

Ionic Compounds
• Most ____________________ compounds have high ____________________ points
• Consider the effect of ____________________ on the melting point when d the
____________________ the ions are separated is about the same.
• NaF (+1 ion x –1 ion) m.p. = 988oC
• CaO (+2 ion x –2 ion) m.p. = 2580 oC

Effect of Distance
Consider the effect of d the ____________________ the ions are separated when the charge is
the same.

Salt Melting Point, oC

NaF 988
NaCl 801
NaBr 755
NaI 651

Intermolecular Forces
Forces ____________________ (rather than within) molecules.
• ____________________ ____________________ attraction: molecules with
dipoles orient themselves so that “+” and “−” ends of the dipoles are close to each other.
• ____________________ ____________________: dipole-dipole attraction in
which hydrogen is bound to a highly electronegative atom. (F, O, N)
Dipole-Dipole Attractions

A Water Molecule

The Boiling Points of the Covalent Hydrides of the Elements in Groups 4A, 5A, 6A, and 7A
London Dispersion Forces
• relatively ____________________ forces that exist among noble gas atoms and nonpolar
molecules. (Ar, C8H18)
• caused by ____________________ dipole, in which electron distribution becomes
asymmetrical.
• the ease with which electron “cloud” of an atom can be distorted is called
____________________.
London Dispersion Forces

Trends in Boiling Points

For similar type substances, there is an _______________ in boiling point with an
_______________ in molecular mass.
Example
Account for the fact that F2 is a gas, Br2 is a liquid, and I2 is a solid at room temperature.

Example
Even though bromine, Br2 gmm = 160 and ICl gmm = 162 have similar molecular masses, their boiling
points are significantly different. The boiling point of Br2 is 59 oC and that of ICl is 97 oC. Account for
this difference.

Example
Even though the molecular mass of H2S is nearly double that of water and even though both H2S and
H2O are polar molecules, the boiling point of H2O is 167 oC higher than that H2S. Account for this vast
difference in boiling points.
Example
Predict the order of decreasing boiling points for the compounds LiF, HF, MgO, He, SiH4, and PH3. Give
reasons for your order.

Some Properties of a Liquid

Surface Tension: The ____________________ to an increase in its surface area (polar
molecules).
Capillary Action: Spontaneous ____________________ of a liquid in a narrow tube.
Viscosity: Resistance to ____________________ (molecules with large intermolecular forces).

Surface Tension

Measure of the inward forces that must be overcome in order to expand the surface area of a liquid

Molecules in a Liquid

Capillary Action
• ____________________ forces- all the forces holding a liquid together.
• ____________________ forces- forces of attraction between a liquid and another surface
• ____________________ Action- occurs if adhesive forces exceed cohesive forces.
Vaporization
• Vaporization is the process by which molecules on the surface of the liquid __________________
into the gas phase
• ____________________ is vaporization in an open container
• ____________________ happens when molecules of vapor collide with the liquid surface and is
captured there.

Equilibrium
When the rate of vaporization equals the rate of condensation in a closed container, the liquid and gas
molecules have achieved a dynamic ____________________.
Liquid ⇌ Vapor
Behavior of a Liquid in a Closed Container

The Rates of Condensation and Evaporation

Vapor Pressure
• is the pressure of the vapor present at ____________________.
• is determined principally by the size of the ____________________ forces in the liquid.
• ____________________ significantly with temperature.
• Volatile liquids have ____________________ vapor pressures.
Vapor Pressure

The Number of Molecules in a Liquid With a Given Energy Versus Kinetic Energy at Two
Temperatures

The Vapor Pressure of Water

Temperature Dependence of Vapor Pressure

Hvap 1
ln (Pvap) = - x + C
R T
R = 8.3145 J/mol K

Example
Determine the H(vap) for water given the following data:

T (oC) P (torr)
0.0 4.579
10.0 9.209
20.0 17.535
25.0 23.756
30.0 31.824
40.0 55.324
60.0 149.4
70.0 233.7
90.0 525.8
Two point slope form:
𝑃𝑣𝑎𝑝𝑇1 ∆𝐻𝑣𝑎𝑝 1 1
ln (𝑃 )= (𝑇 - 𝑇 )
𝑣𝑎𝑝𝑇2 𝑅 2 1

Example
The vapor pressure of water at 25 oC is 23.8 torr, and the heat of vaporization of water at 25 oC is 43.9
kJ/mol. Calculate the vapor pressure of water at 50. oC

Boiling Point
Constant temperature when added energy is used to vaporize the liquid.

vapor pressure of liquid = pressure of surrounding atmosphere

Heating Curve for Water

Melting Point
Molecules break loose from ____________________.points and solid changes to liquid.
(Temperature is ____________________.as melting occurs.)
vapor pressure of solid = vapor pressure of liquid
Phase Diagram
Represents phases as a function of ____________________.and ____________________.
critical ____________________.: temperature above which the vapor can not be liquefied.
critical ____________________.: pressure required to liquefy AT the critical temperature.
critical ____________________.: critical temperature and pressure (for water, Tc = 374°C and 218
atm).

Phase Diagram for Carbon Dioxide The Phase Diagram for Water

Types of Solids

____________________.Solids: highly ____________________.arrangement of their

components [table salt (NaCl), pyrite (FeS2)].
____________________.solids: considerable ____________________.in their
structures (glass).

Types of Crystalline Solids

____________________.Solid: contains ions at the points of the lattice that describe the structure of
the solid (NaCl).

____________________.Solid: discrete covalently bonded molecules at each of its lattice points

(sucrose, ice).

____________________.Solid: atoms at the lattice points.

• ____________________.solids- metallic bonding
• ____________________.solids- covalent bonding (diamond)
Examples of Three Types of Crystalline Solids

Representation of Components in a Crystalline Solid

Lattice: A 3-dimensional system of points designating the centers of components (atoms, ions, or molecules)
that make up the substance.

Analysis of Solids

• Structures of crystalline solids determined by ____________. _________________.analysis

• ____________________.occurs when beams of X-rays are shined on a pure crystal.

• Waves add constructively (in phase) and destructively (out of phase)

• Whether waves add in phase or out of phase depends on the difference in the distance traveled after they
strike the atoms of the crystal

Interference of Light Rays

Bonding Models for Metals

____________________.: A regular array of metals in a “sea” of electrons.

____________________.: Electrons assumed to travel around metal crystal in MOs formed

from valence atomic orbitals of metal atoms.
The Electron Sea Model for Metals Postulates a Regular Array of Cations in a “Sea” of Valence
Electrons

Metal Alloys
1. ____________________.Alloy: some metal atoms replaced by others of similar size.
brass = Cu/Zn
2. ____________________.Alloy: Interstices (holes) in closest packed metal structure are
occupied by small atoms.
steel = iron + carbon
3. Both types: Alloy steels contain a mix of substitutional (carbon) and interstitial (Cr, Mo) alloys.

Two Types of Alloys

Network Solids
Composed of strong directional covalent bonds that are best viewed as a “giant molecule”.
•
•
•

Examples: graphite, diamond, ceramics, glass

The Structures of Diamond and Graphite

A Gas
•
•
•
•
•
•

Pressure
•
•
•
•
▪

A Torricellian Barometer (image at right)

At sea level, latitude 45o north (or south), the average atmospheric pressure supports a column of
mercury 760 mm high in a simple mercury barometer at 0oC This average pressure is called one
atmosphere.
The Effects of Decreasing the Volume of a Sample of Gas at Constant Temperature

Boyle’s Law
• V ∝ 1/P (T = constant)
• P1V1 = P2V2 (T = constant)

Plotting Boyle’s Data

• A plot of ________________.v ________________.presents a graph with a curve
• A plot of ________________.v ________________. presents a graph with a straight line, showing an
inverse relationship
• A gas that strictly obeys Boyle’s Law is called an ____________________.gas.

Example: Boyle’s Law

• At 25oC, a sample of oxygen occupies 100. mL under a pressure of 380. torr. What volume would it
occupy under a pressure of 1.00 atm at the same temperature?
Answer
•

Example
• At 100.oC a sample of neon occupies 200. mL under a pressure of 4.00 atmospheres. What must the
pressure be for it to occupy 800. mL at 100.oC?
Answer
•
The Effects of Increasing the Temperature of a Sample of Gas at Constant Pressure

Charles’s Law
• The volume of a gas is directly proportional to temperature, and extrapolates to zero at zero Kelvin.
• V ∝ T (P = constant)
𝑉1 𝑉2
• = (P = constant)
𝑇1 𝑇2

Amazing
• Experiments have shown that when a 273 mL sample of gas at 0 oC is heated to 1 oC, its volume
increases by 1 mL to 274 mL. Conversely each degree the gas is cooled its volume decreases 1 mL.
What will the volume of the gas be at –273 oC?

Plots of V Versus T (ºC) for Several Gases

The Kelvin Temperature Scale

• The temperature at –273 oC, the lowest temperature possible is known as
____________________.____________________.. It is the basis of the Kelvin (absolute) temperature.
• K=
Plots of V Versus T

Example Charles’ Law

• A sample of hydrogen, H2, occupies 100. mL at 25 oC and 740. torr. What volume would it occupy
at 50.0 oC and 740. torr?

Answer
•

Example
• A sample of oxygen, O2, occupies 200. mL at 100. oC and 1.00 atm. At what temperature (oC) will
the oxygen occupy 400. mL if the pressure remains constant?

Answer
•

The Effects of Increasing the Temperature of a Sample of Gas at Constant Volume:

Who’s Law?

Gay-Lussac’s Law
• P ∝ T (V = constant)
𝑃1 𝑃2
• = (V = constant)
𝑇1 𝑇2
Combined Gas Law
• Boyle’s and Charles’ Laws can be combined together into the following mathematical expression:
•

A very convenient form:

•
• The relationship has six variables. If any five are known, the sixth can be calculated.

Example
• A sample of nitrogen, N2, occupies 200. mL at 57 oC under a pressure of 840. torr. What volume
would it occupy at 0 oC and 1.00 atm pressure?

Answer
•

Example
• A sample of methane, CH4, the main component of natural gas occupies 400. mL at 96 oC under a
pressure of 0.500 atm. What volume would it occupy at 0 oC under a pressure of 1200 torr?

Answer
•

Avogadro’s Law
• For a gas at constant temperature and pressure, the volume is directly proportional to the number of
moles of gas (at low pressures).
• V = an
o a = proportionality constant
o V=
o n=

Modern Combined Gas Law

• Avogadro’s hypothesis can be incorporated into the combined gas law:
•

Standard Temperature and Pressure (STP)

• P=
• T=
• The molar volume of an ideal gas is ____________________. liters at STP
A Mole of Any Gas Occupies a Volume of Approximately 22.4 L at STP

Example
• What volume does 36.3 g of oxygen, O2, occupy at STP?

Answer

Molecular Weight
• Application of the gas laws provides a method of calculating the molecular weight of a gas.
• This plus elemental analysis provides mechanism for determining molecular formula

Example
• If 2.00 g of a gas occupies 560.mL at STP, what is its molecular weight?
•
• Answer

• Molar Mass =

Example
• A compound containing only carbon and hydrogen is 80.0% C and 20.0% H by mass. At STP 280.
mL of the gas weighs 0.375 g. What is the molecular formula for the compound?

Answer
Ideal Gas Law
• An equation of state for a gas.
• “state” is the condition of the gas at a given time.
• Can be determined by combining Boyle’s Law, Charles’ Law, and Avogadro’s Law
• ________________________________________.
o R = proportionality constant = 0.0821 L atm K-1 mol-1
o P = pressure in atm
o V = volume in liters
o n = moles
o T = temperature in Kelvins
o Holds closely at P < 1 atm

Example
• What volume does 48.0 g of methane, CH4, occupy at 140. oC under a pressure of 1280 torr?

Answer
•

Example
• A 250. mL flask contains a mixture of nitrogen, oxygen, and helium at a temperature of 27 oC and a
pressure of 0.850 atm. How many moles of gas are present?

Answer
•

Example
• What pressure in kilopascals is exerted by 0.480 g of carbon dioxide in a 1.00 L flask at 100.oC?

Answer
•

Density
• Density has the units of mass per unit volume. We can arrange the ideal gas equation to obtain
density
𝑃𝑀
• D = 𝑅𝑇
o M is the gram molar mass
o D is is g/L
 Example
• What is the density of formaldehyde, CH2O, vapors at 95 oC and a pressure of 650. torr?

Answer
•

Gram Molecular Mass

• The Ideal Gas Equation can be rearranged to solve directly for gram molecular mass.
𝑚𝑅𝑇
• M = 𝑃𝑉

Example
• A 0.1842 g sample of phosphorus vapor in a 169 mL bulb exerts a pressure of 45.6 kPa at 350. oC.
Calculate both the molecular mass and molecular formula of phosphorus vapor. (R = 8.31 kPa L/
mol K)

Answer
•

Dalton’s Law of Partial Pressures

• For a mixture of gases in a container,
• PTotal =

Partial Pressure of Each Gas in a Mixture

Example
• If 100 mL of hydrogen and 100. mL of oxygen, both measured at 25 oC and 1.00 atm pressure, were
forced into one of the containers at 25 oC, what would be the total pressure of the two gases?

Answer
•

Collecting Gas Over Water

• A gas can be collected by displacement of water
• This results in a mixture of gases:
o
o
• Vapor pressure is ____________________.dependent.
• Ptotal =
• How do we correct for the water vapor?

Example
• A sample of solid potassium chlorate (KClO3) was heated in a test tube and decomposed by the
following reaction:
2KClO3(s) → 2 KCl(s) + 3O2(g)
The oxygen produced was collected by displacement of water at 22.0 °C at a total pressure of 754
torr. The volume of the gas collected was 0.650 L, and the vapor pressure of the water at 22.0°C is
21 torr. Calculate the partial pressure of O2 in the gas collected and the mass of KClO3 in the sample
that was decomposed.

Solution / Answers
Kinetic Molecular Theory
• Gases consist of tiny discrete molecules that are relatively _____________._________________..
• Gases consist of molecules in continuous ____________________.____________________..
• Molecular ____________________.are ____________________.
• The average kinetic energy of gaseous molecules is ____________________.to the absolute
temperature. KE = ½ mv2

Examples
• Explain Gay Lussac’s Law on the basis of the Kinetic Molecular Theory (please draw a diagram to
illustrate your answer)

Answer
•

• Explain Boyle’s Law on the basis of the Kinetic Molecular Theory (please draw a diagram to
illustrate your answer)

Answer
•

• Explain Charles’ Law on the basis of the Kinetic Molecular Theory (please draw a diagram to
illustrate your answer)

Answer
•

Real Gases
• At ordinary temperatures and pressures, most gases obey the gas laws reasonably well.
• Under what conditions does a gas deviate significantly form ideality? Why?
• Must correct ideal gas behavior when at ____________._______________.
(_______________._______________.) and _______________._______________. (attractive
forces become ____________________.).
• At high pressures and low temperatures gas particles come close enough to one another to make two
postulates of the kinetic molecular theory invalid.
o The assumption that gases are composed of tiny particles whose size is negligible compared
to the average distance between them begins to fail –
▪ When the gas is pressurized into a small space the gas particles size becomes
____________________.____________________.compared to the total volume.
o The assumption that the forces of attraction or repulsion between two particles in a gas are
very weak or negligible begins to ____________________.. – Low temperature means less
energy, so the particles are ____________________.to one another ________________..
• Under these conditions (high P and low T), gases are said to behave non-ideally or like ‘real’ gases.
This has two consequences.
o When gases are under high pressures, the size of the gas particles is no longer negligible
compared to the total space occupied by the gas (its total volume). So, the observed total
volume occupied by the gas under these real conditions is artificially large since the gas
particles are now occupying a significant amount of that total volume.
o The actual pressure of a gas is lower than one would expect when assuming there were no
attractive forces between the particles. In a real gas, because the particles are attracted to one
another, they collide with the walls with less force, and the observed pressure is less than in
an ideal gas.
• Correction Equation: van der Waals Equation – you will not need to use this, but it is shown to
illustrate the corrections for real conditions.

The Meaning of Temperature

3
• (KE)avg = 2RT
• Kelvin temperature is an index of the ____________________.____________________.of gas particles
(higher T means greater motion.)

A Plot of the Relative Number of O2 A Plot of the Relative Number of N2

Molecules That Have a Given Velocity at Molecules That Have a Given Velocity at
STP Three Temperatures

Aqueous Solutions
• Water is the dissolving medium, or ____________________..

Figure 4.1 The Water Molecule is Polar

Some Properties of Water
•
•
•
•

A Solute
•
•
•

A Solvent
•
•

Polar Water Molecules Interact with the Positive and Negative Ions of a Salt

BaCI2 Dissolving

Polar Water Molecules Interact with the polar bonds of a molecular solute (ethanol)

Electrolytes
• Electrolytes are substances that will ____________________.an
____________________.____________________.in ____________________.solution
• Knowledge of electrolytes will enable us to make powerful predictions about metathesis reactions.
• ____________________.- conduct current efficiently
o NaCl, HNO3
• ____________________.- conduct only a small current
o vinegar, tap water
• ____________________.- no current flows
o pure water, sugar solution
Strong Electrolytes
• Soluble salts- eg. NaCl, Pb(ClO3)2
• Strong acids- eg. HCl, H2SO4
• Strong bases- eg. NaOH, KOH

Weak or Nonelectrolytes
• Insoluble or only slightly soluble salts. Eg. AgCl, CaSO4
• Weak Acids- eg. CH3COOH, HF
• Weak Bases- eg. NH3, amines
• Water

Acids
• Strong acids - ionized completely to produce H3O+ in solution
o HCl + HOH → H3O+ + Cl-
• Weak acids - ionize to a slight extent to give H3O+ in solution so NOT strong electrolytes!
o CH3COOH + HOH H3O+ + CH3COO-

HCI (aq) is Completely Ionized Acetic Acid in Water

Remember Strong Acids - If it is not strong it is weak!

• HCl, HBr, HI. Not HF (weak)
• H2SO4
• HNO3
• HClO3, HBrO3, HIO3
• HClO4

Bases
• Strong bases - dissociate completely in water to give OH ions. NaOH, KOH, LiOH
𝐻2𝑂
o NaOH → Na+ + OH-
• Weak bases - ionize only slightly with water to give OH- ions. NH3 is our model weak base
o NH3 + HOH ⇌ OH- + NH4+
Solution of Sodium Hydroxide The Reaction of NH3 in Water

Common Terms of Solution Concentration

• ____________________.- routinely used solutions prepared in concentrated form.
• ____________________.- relatively large ratio of solute to solvent. (5.0 M NaCl)
• ____________________.- relatively small ratio of solute to solvent. (0.01 M NaCl)

Molarity
• Molarity (M) = :
• M = Molarity =

Example
• Calculate the molarity of a solution that contains 200. g of MgCl2 in 1.00 L of solution.

Answer

Example
• Calculate the mass of solute required to make 750. mL of a 2.50 M sodium chloride solution

Answer
•

Standard Solution
• Solution whose concentration is accurately known. Procedure involves the use of a volumetric flask.
Preparation of a Standard Solution

Example
• Calculate the number of grams of potassium permanganate necessary to make 1.00 L of a 0.0200 M
solution. (molar mass of KMnO4 = 158 g/mol)

Answer
•

Dilution
• Standard solutions can be diluted to desired concentrations
• Moles of solute after dilution = moles of solute before dilution
o
• Procedure involves the use of volumetric (or calibrated) pipets and volumetric flasks

Calibrated (measuring) Pipet and a Volumetric(transfer) Pipet

Example
• Make a 0.0500 M solution of Hydrochloric acid from 250. mL of 2.00 M HCl solution. How many
milliliters of solution will you have?

Answer
•

Example
• Calculate the volume of 0.020 M KMnO4 solution needed to make 1.0 L of 0.015 M solution

Answer
•

Separation Techniques
•
•
•

Chromatography
Chromatography is a technique for
• ____________________.mixtures of compounds
• ____________________.unknown compounds
• establishing the ____________________.or concentration of compounds
• monitoring product formation in the pharmaceutical and biotechnology industries
• Uses a system with two phases (states) of matter:
o ____________________.phase- liquid or gas
o ____________________.phase - solid
• The separation process occurs because the components of the mixture have different
____________________.for the two phases and thus move through the system at different rates.
• A component with a high affinity for the mobile phase moves relatively
____________________.through the chromatographic system
• A component with a high affinity for the solid phase moves more ____________________.

Chromatography Example
• A black dot of ink is placed on a piece of chromatography paper and placed into a beaker with
solvent.
• The paper will serve as a wick for the solvent.
• The components of the ink (different dyes) will travel up the paper at different rates based on
affinities for the solvent or for the paper.
• Chromatography of Ink

Filtration
• A method of separation used with the mixture consists of a solid and a liquid. The mixture is poured
onto a mesh, such as filter paper, which passes the liquid and leaves the solid behind.

Distillation
• A process that depends on differences in the ____________________.points of the components.
• In simple distillation, a mixture is heated in a device (shown on next slide).
• The most ____________________.component (the one that boils at the lowest temperature)
vaporizes at the lowest temperature, and the vapor passes through a cooled (a condenser), where it
condenses back into its liquid state and collected.

Simple Laboratory Distillation Apparatus

Spectroscopy
Spectroscopy is the study of the interaction of electromagnetic radiation and matter.
• ____________________.Spectroscopy
• ____________________.Spectroscopy
• ____________________.Spectroscopy
• ____________________.Spectroscopy

Absorption Spectroscopy
• Absorption spectroscopy involves a sample being exposed to radiation of varying types, and then
observing what happens as the sample ____________________.with the radiation. Depending on the
type of radiation used, information about the substance can be gathered.

UV and Visible Spectroscopy

• Ultraviolet (UV) and visible spectroscopy (PES) (relatively short wavelengths)
• As in PES, UV and visible light tends to cause
____________________.tran____________________.sitions within atoms, so can be used to
gather information about ____________________.____________________..

Infrared (IR) Spectroscopy

• When covalent bonds are exposed to infrared radiation they absorb that energy and tend to bend,
____________________.and ____________________.. The interaction with the IR is unique for
each type of bond, so IR spectroscopy can be used to distinguish between compounds that have
different types of ____________________.____________________..

Microwave Spectroscopy
• ____________________.____________________.can be caused by the use of microwaves, and can
be used to determine the chemical ____________________.and ____________________.of
molecules.

Beer’s Law
• Beer’s Law utilizes UV Spectroscopy to examine how much light is ____________________.by a
compound’s sample at various ____________________..
• Spectrum peaks indicate the ____________________.associated with electrons’ energies in a
compound (how much energy is absorbed).
• It is mainly used to determine a sample’s ____________________.when that concentration is
unknown.
• Relates ____________________.and ____________________.
• Enables a sample’s concentration to be determined based on its absorbance value
• A= εbc
o A= absorbance
o ε= molar absorptivity (molarity-1 centimeters-1)
o b = path length
o c = concentration (molarity, M)

Beer’s Law – Path Length

• How far electromagnetic radiation must travel through a sample
• Unit – centimeters (cm)
• Increased length, radiation hits more molecules and leads to higher absorbance
Beer’s Law - Analysis
• Analyzing Absorbance Data
o Form a standard curve based on absorbance measurements of standards solutions with
KNOWN concentrations at a specific wavelength
o Plot absobance vs concentration graph – standards Beer’s Law Plot
▪ Generates a straight line
o Slope of line = ∆A / ∆C
▪ eb = constant SO can find concentration of unknown sample with absorbance
measurement