Che Calc

Chemistry 1B - Foothill College
Intermolecular Forces, Liquids, and Solids

Understand intermolecular forces (IMF). Be able to determine the type(s) of IMF that exist for various substances. Understand properties of liquids and solids and how IMF effect these properties. Learn about the structure of solids and understand the difference between crystalline and amorphous solids. Understand the concepts of crystal lattice and cubic unit cells (LAB). Understand the different types of attractive forces in crystalline solids and how these forces effect the properties of solids.
1
Intermolecular Forces, Liquids and Solids
The States of Matter: Macroscopic Properties
L. J. Larson- All rights reserved
States of Matter: Microscopic View

A fundamental difference between states of matter is the distance between particles. In the solid and liquid states particles are closer together, thus we refer to them as condensed phases.
The strength of attractive forces between particles (atoms, ions or molecules) determines a substances phase at room temperature.
The States of Matter

The state a substance is in at a particular temperature and pressure depends on two antagonistic entities:
! The kinetic energy of the particles
! The strength of the attractions between the particles
Intermolecular Forces (IMF): Net Electrostatic Attractive Force BETWEEN Molecules Directly related to properties such as melting point, boiling point and the energies to overcome the forces of attraction between particles in changes of state (!Hfus and !Hvap). Determines solubility of gases, liquids and solids in various solvents. Crucial in determining the structure of biological macromolecules such as DNA and proteins. IMF are short-range forces. They only exist over short (nm) distances.
Intermolecular Forces, Liquids and Solids 6
Energy and Intermolecular Forces

Energy is required to overcome intermolecular forces in a liquid to make a gas. This energy is the heat of vaporization, !Hvap.
Intermolecular Forces
Intermolecular forces (IMF) as a group are generally referred to as van der Waals forces. These attractions are not nearly as strong as the intramolecular attractions that hold atoms together in compounds: Lets list approximate energies for the following: Covalent Bond Energies: Lattice Energies: Intermolecular Force (IMF) Energies:
Intermolecular Forces
IMF are, however, strong enough to control physical properties such as:
They are also responsible for deviations in ideal behavior of gases.

9
van der Waals Forces Include

Dipole-dipole interactions Hydrogen bonding London dispersion forces
10
Dipole-Dipole Interactions (d-d)

Molecules that have permanent dipoles are attracted to each other.
! The positive end of one is attracted to the negative end of the other and vice-versa. ! These forces are only important when the molecules are close to each other.
Examples:
11
Dipole-Dipole Interactions
For molecules of about the same molecular weight, what can you conclude about the relationship between boiling point and molecular polarity? Can you explain this trend in terms of intermolecular forces?
12
London Dispersion Forces
While the electrons in the 1s orbital of helium would repel each other (and, therefore, tend to stay far away from each other), it does happen that they occasionally wind up on the same side of the atom. At that instant, then, the helium atom is polar, with an excess of electrons on the left side and a shortage on the right side. An instantaneous dipole results.
13
Another helium nearby, then, would have a dipole induced in it, as the electrons on the left side of helium atom 2 repel the electrons in the cloud on helium atom 1. London dispersion forces, or dispersion forces, are attractions between instantaneous dipoles.

(induced dipole-induced dipole, id-id)
These forces are present to some degree in all molecules, whether they are polar or nonpolar. The tendency of an electron cloud to distort in this way is called polarizability. Define Polarizability:
15
Factors Affecting London Forces
From the above data, what can you conclude about the relationship between molecular weight and strength of London Forces? Can you explain this relationship in terms of polarizability?
16
Factors Affecting London Forces

n-pentane neopentane
What can you conclude about the relationship between molecular shape and the strength of London Forces? Why do you think shape has this effect?
17
Br2 & I2
Br2 is a liquid at RT while I2 is a solid. Why?
18
Dipole - Induced Dipole IMF (d-id)

A polar molecule will induce a TEMPORARY dipole in a nonpolar molecule. The two molecules are now attracted momentarily. This is typically a weaker interaction than d-d.
Is this type of intermolecular force important to fish and other aquatic life?
19
Nonpolar gases are slightly soluble in water.
Can you explain the trend in solubility shown above in terms of IMF?
What would you predict for the solubility of He(g) compared to the above gases?
20
Which Have a Greater Effect:

Dipole-Dipole Interactions or Dispersion Forces?
If two molecules are of comparable size and shape, differences in dipole-dipole interactions will likely be the dominating force. Example: If one molecule is much larger than another, dispersion forces will likely determine differences in their physical properties. Example:
21
How Do We Explain This?

Boiling points of some simple hydrogen compounds.
Why do these compounds have such a high boiling point?
The nonpolar series (SnH4 to CH4) follows the expected trend: as molecular mass decreases, boiling point decreases. The polar series follow the same trend from periods 5 to 3, but the period 2 hydrocarbons are anomalies. Show H-bond video.
22
Hydrogen Bonding - A special case of d-d IMF.

The interaction can be described as:
hydrogen bond
XH ----- :Y
Here X is either a F, O or N atom and Y is a small highly electronegative atom (N, O or F) that has a lone pair of electrons. When a molecule contains one of the following groups of atoms it can hydrogen bond: ! O-H ! N-H ! F-H These groups are highly polar, the exposed H atom has almost a full +1 charge. The resulting interaction of the H atom with a lone-pair of electrons on a small, highly electronegative (N, O or F) adjacent atom gives an unusually strong d-d IMF. We call this a hydrogen bond.
Hydrogen Bonding
A hydrogen bond
NOT a hydrogen bond
Note: Hydrogen bonds are intermolecular forces. They are NOT covalent bonds!
24
Hydrogen bonding in ice.
Does this explain why ice is less dense than liquid water?
25
Hydrogen bonding in acetic acid molecules. Notice how each molecule makes two hydrogen bonds.
26
DNA & hydrogen bonding
double helix
H-bonds
phosphate-sugar backbone
27
Ethanol & diethyl ether

Ethanol and diethyl ether are structural isomers. Predict which substance has the greater boiling point.
28
Ion-Dipole Interactions
A fourth type of force, ion-dipole interactions are an important force in solutions of ions. The strength of these forces are what make it possible for ionic substances to dissolve in polar solvents. Examples:
29
Summarizing Intermolecular Forces
30
Like-Dissolves-Like!
Compounds with similar IMF are usually soluble in one another. This will be covered in more detail in Chemistry 1C, Chapter 13.
31
Problem
What IMF exist in the following systems? ! Pure CH4 ! Water and CH3OH ! F2 and water
! HCl and CH3OCH3
Rank the above systems in order of increasing strength of IMF

32
Intermolecular Forces Affect Many Physical Properties

The strength of the attractions between particles can greatly affect the properties of a substance or solution.
Liquids: Behavior is more difficult to describe compared to gas behavior. Short-range order but no long-range order Some properties of liquids: ! Viscosity ! Surface Tension ! Capillary Action ! Heat of vaporization ! Vapor Pressure ! Boiling Point ! Critical Temperature and Pressure
Viscosity
Resistance of a liquid to flow is called viscosity. (SI units kg/m-s) It is related to the ease with which molecules can move past each other. What does viscosity depend upon?
34
Glycerol
Which would you predict to have the greater viscosity, glycerol or ethanol, CH3CH2OH? Explain.
O C
35
Surface Tension
Surface tension results from the net inward force experienced by the molecules on the surface of a liquid. Surface tension is the energy needed to increase the surface area of a liquid by a unit amount. Examples are: Water at 20C 7.29x102 J/m2 Mercury at 20C 4.6x101 J/m2 What does surface tension depend upon?
36
Capillary Action:
adhesive forces.
Adhesive forces:
the ability of liquids to rise in tubes through
Cohesive forces:
37
Phase Changes
38
Energy Changes Associated with Changes of State

Stronger IMF generally result in higher !Hfus and !Hvap.
Heat of Fusion: Heat of vaporization: Using information from the above graph, what is the heat of sublimation of butane?
39
Energy Changes Associated with Changes of State

Heating Curve for water The heat added to the system at the melting and boiling points goes into pulling the molecules farther apart from each other. The temperature of the substance does not rise during the phase change.
What segments of the curve correspond to an increase in potential energy of the system?
What segments of the curve correspond to an increase in kinetic energy of the system?
Show change in state video.

40
Text Problem 11.37: Drinking water can be cooled in hot climates by evaporating it from the surfaces of canvas bags or porous clay pots. How many grams of water can be cooled from 35C to 22C by the evaporation of 50.0 g of water. The heat of vaporization of water in this temperature range is 2.4 kJ/g and the specific heat capacity of water is 4.18 J/g-K.
Which do you expect to have the greatest heat of vaporization? NH3 or PH3? Cl2 or I2?
41
Evaporation and Temperature

At any temperature, some molecules in a liquid have enough energy to escape into the gas phase. As the temperature rises, the fraction of molecules that have enough energy to escape increases.
42
Vapor Pressure of a Liquid

As more molecules escape the liquid, the pressure they exert as a gas increases. The liquid and vapor reach a state of dynamic equilibrium: liquid molecules evaporate and vapor molecules condense at the same rate. !Define Vapor Pressure of a liquid:
!Vapor Pressure depends upon: !Vapor Pressure does not depend upon:
Vapor Pressure of Butane
Show vapor pressure as a function of temperature video
44
Boiling Point
The boiling point of a liquid is the temperature at which its vapor pressure equals the external pressure exerted upon the liquid. The normal boiling point is the temperature at which a liquids vapor pressure is 760 torr (1 atm).
Estimate the boiling point of water at: 600 mm Hg
1000 mm Hg
45
Problem:
What is the vapor pressure of CS2 at 40 C? What is the normal boiling point of CS2? What IMF are present for each compound? Which compound has the strongest IMF? Which liquid would have the lowest !Hvap?
46
Critical Temperature and Pressure

Critical Temperature:
Critical Pressure:
Which of these substances can be liquefied at room temperature, about 20C?
47
Solids
We can think of solids as falling into two groups: (1) Crystalline (2) Amorphous ! Crystallineparticles (atoms, molecules or ions) are in highly ordered three dimensional arrangement: Ionic Metallic Molecular Network covalent ! Pure crystalline solids exhibit sharp melting points.
Solids
! Amorphousno particular order in the arrangement of particles. ! Amorphous solids do not exhibit sharp melting points. Instead, their temperature changes as they melt.
49
Crystalline Solids
The particles (atoms, ions or molecules) can be represented by a 3-dimensional array of points called a crystal lattice. Because of the order in a crystal, we can focus on the repeating pattern of arrangement called the unit cell.
50
Crystalline Solids: Overview of cubic unit cells covered in more detail in lab.
There are several types of basic arrangements in crystals, such as the ones shown above.
51
Types of Bonding in Crystalline Solids
52
Ionic Solids
Ionic forces of attraction Positive and negative ions Melting point tends to increase with increasing lattice energy.
Example: List in order of increasing mp; CaO, NaCl and KI
Properties Hard - brittle High melting points Poor electrical conductors as solid, good as liquid Many are water soluble. Aqueous solutions conduct electricity.
Cl ions primitive with Cs+ ions in center
S2 ions fcc with the Zn2+ ions in half the tetrahedral holes
Ca2+ ions fcc with the F ions in all tetrahedral holes 53
Ionic Solids
What are the empirical formulas for these compounds? (a) Green: chlorine; Gray: cesium (b) Yellow: sulfur; Gray: zinc (c) Green: calcium; Gray: fluorine
(a)
(b)
(c)
CsCl
ZnS
CaF2
54
Covalent-Network Solids
Atoms held together in large networks of strong covalent bonds Properties Hard High melting points Poor electrical and thermal conductors (usually)*
3.41 dispersion forces hold layers together
mp = 3550C
1.42 covalent bonds

*Graphite is a good conductor of electricity along
the layers due to the delocalized " bond system 55
The unit cell for diamond is shown here.

What type of unit cell is this?
56
Covalent-Network Solids-Other Examples

Silicates - quartz, sand, etc.
SiO2 lattice
57
Molecular Solids
Forces of attraction are Dispersion Dipole-dipole Hydrogen bonds Properties Fairly soft Low to moderate melting points Poor electrical and thermal conductors
Ice -a molecular solid
58
Metallic Solids
Metals are not covalently bonded, but the attractions between atoms are too strong to be van der Waals forces. In metals, valence electrons are delocalized throughout the solid. Metallic forces of attraction (bonding):
Electron Sea Model

Attraction between positive cores and a sea of valence electrons resulting in bonding that is non-directional in nature.
59
Metallic Solids
Metallic Properties Malleable Ductile Good electrical and heat conductors Wide range of hardness Wide range of melting points, but many have high melting points
Al is FCC
60
Amorphous Solids
Properties Non crystalline Wide range of melting points Poor electrical conductors
Glass
61
Examples of Some Physical Properties of Solids

Substance
Metallic Bonding
Ionic Bonding
62
Example Problems
Rank in order if increasing melting point: CH3F, MgO, H2 O and CsI
For each of the following pairs, predict which will have the higher melting point and explain why. (a) HF or HCl (b) CH4 or CCl4 (c) KBr or H2O
Given the following solids: BaCl2 , Zn, CH3COOH and diamond Which would conduct electricity? Which would dissolve in water to give a solution that conducts electricity? Which would be malleable? Which would be brittle? Which would have the lowest melting point?
63
Example Text Problems

11.7 Niobium (II) oxide crystallizes in the following cubic unit cell.
(a) How many niobium atoms and how many oxygen atoms are within the unit cell? (b) What is the empirical formula of niobium oxide? (c) Is this a molecular, covalent-network, or ionic solid?
64

11.16abd What type of intermolecular force accounts for the following differences in each case? (a) CH3OH boils at 65C, CH3SH boils at 6C.
(b) Xe is liquid at atmospheric pressure and 120 K, whereas Ar is a gas.
(d) Acetone boils at 56C, whereas 2-methylpropane boils at !12C.
65

11.48 Explain the following observations: (a) Water evaporates more quickly on a hot, dry day than on a hot, humid day.
(b) It takes longer to cook hard-boiled eggs at high altitudes than at lower altitudes.
66

11.102ab Liquid butane, C4H10, is stored in cylinders, to be used as a fuel. The normal boiling point of butane is listed as !0.5C. (a) Suppose the tank is standing in the sun and reaches a temperature of 46C. Would you expect the pressure in the tank to be greater or less than atmospheric pressure? How does the pressure within the tank depend on how much liquid butane is in it? (b) Suppose the valve to the tank is opened and a few liters of butane are allowed to escape rapidly. What do you expect would happen to the temperature of the remaining liquid butane in the tank? Explain.
67

Che Calc

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Che Calc

Uploaded by

Copyright:

Available Formats

Chemistry 1B - Foothill College

Intermolecular Forces, Liquids, and Solids

Intermolecular Forces, Liquids and Solids

The States of Matter: Macroscopic Properties

Intermolecular Forces, Liquids and Solids

L. J. Larson- All rights reserved

Chemistry 1B - Foothill College

States of Matter: Microscopic View

Intermolecular Forces, Liquids and Solids

Intermolecular Forces, Liquids and Solids

L. J. Larson- All rights reserved

Chemistry 1B - Foothill College

The States of Matter

! The strength of the attractions between the particles

Intermolecular Forces, Liquids and Solids

L. J. Larson- All rights reserved

Chemistry 1B - Foothill College

Energy and Intermolecular Forces

Intermolecular Forces, Liquids and Solids

L. J. Larson- All rights reserved

Chemistry 1B - Foothill College

They are also responsible for deviations in ideal behavior of gases.

Intermolecular Forces, Liquids and Solids

van der Waals Forces Include

Intermolecular Forces, Liquids and Solids

L. J. Larson- All rights reserved

Chemistry 1B - Foothill College

Dipole-Dipole Interactions (d-d)

Intermolecular Forces, Liquids and Solids

Intermolecular Forces, Liquids and Solids

L. J. Larson- All rights reserved

Chemistry 1B - Foothill College

London Dispersion Forces

Intermolecular Forces, Liquids and Solids

London Dispersion Forces

L. J. Larson- All rights reserved

Chemistry 1B - Foothill College

London Dispersion Forces

Intermolecular Forces, Liquids and Solids

Factors Affecting London Forces

Intermolecular Forces, Liquids and Solids

L. J. Larson- All rights reserved

Chemistry 1B - Foothill College

Factors Affecting London Forces

Intermolecular Forces, Liquids and Solids

Intermolecular Forces, Liquids and Solids

L. J. Larson- All rights reserved

Chemistry 1B - Foothill College

Dipole - Induced Dipole IMF (d-id)

Intermolecular Forces, Liquids and Solids

Nonpolar gases are slightly soluble in water.

Intermolecular Forces, Liquids and Solids

L. J. Larson- All rights reserved

Chemistry 1B - Foothill College

Which Have a Greater Effect:

Intermolecular Forces, Liquids and Solids

How Do We Explain This?

Why do these compounds have such a high boiling point?

Intermolecular Forces, Liquids and Solids

L. J. Larson- All rights reserved

Chemistry 1B - Foothill College

Hydrogen Bonding - A special case of d-d IMF.

NOT a hydrogen bond