Humboldt State University ® Department of Chemistry

Richard A. Paselk

Chem 109 - General Chemistry - Spring 2013

Lecture Notes 32: 22 April


Liquids & Solids, cont.

Liquids: cont.,

  • Freezing
    • freezing/melting point: temperature at which solid and liquid are in equilibrium.
    • heat of fusion/crystallization
    • supercooling (occurs because its hard to "seed" crystals - will see later when solids are discussed)
      • Glasses: supercooled "solid" liquids.
  • Heating/cooling curves, below.
  • Viscosity
    • due to van der Waals forces and long molecules
    • due to strong H-bonding (ethylene glycol, HOCH2CH2OH has a viscosity much like high MW syrup)
  • Surface Tension: due to attraction of molecules of liquid for each other (diagram).
    • meniscus
  • detergents/surfactants and wetting (water striders, ducks etc.)

Weak Bonds

Weak bonds range from about 10% as strong as a covalent or ionic bond to <1% as strong. Note the examples in the table below:

 Interaction Type
Example Average Strength, kcal/mol (kJ/mol) Range**
Charge-dipole -NH3+ Cl-   1/r2
Dipole-dipole ClCH3 ClCH3    1/r3
Dipole-induced dipole* CH4 ClCH3 0.1-0.2 (0.4-4)  1/r6
(induced dipole-induced dipole)

0.1-0.2 (0.4-4)
Hydrogen bond  Hydrogen bonded water dimer 3-8 (12-30)  

 van der Waals repulsion
*van der Waals interactions, **from Zubay Biochemistry 3rd. Table 4.3, pg. 89.
The van der Waals bonds are strictly the dipole-induced dipole and dispersion types, but is also often used to refer to other weak bonds other than hydrogen bonds. Notice that the bonds are not only very weak (about 0.1 - 0.3% as strong as a covalent bond), they also do not act at a distance. Essentially they are contact bonds - they sort of act like a weak tape. The corollary is that they increase in importance with increases in molecular size (and thus contact surface).

Thus for hydrocarbons, which are essentially completely non-polar, we see a very low boiling point for methane (CH4) of - 161°C and a fairly regular increase in boiling point as carbons are added (ethane, C2H6 - 88°C; butane, C4H10 - 0.5°C; hexane, C6H14 69°C; octane, C8H18 126°C; etc.) until very large molecules such as paraffin (about 100 C's) and polyethylene (>1,000 C's) are essentially non-volatile. Note also though, in these very large molecules the forces holding the substance together have become significant due to the very large contact areas.

Hydrogen bonds are a special case of weak bonds. Note that they are significantly stronger (>100 fold) than the other weak bonds at about 4-10% as strong as a covalent bond. Hydrogen bonds only occur when a hydrogen bound to a small, very electronegative atom is brought close to another small, very electronegative atom. Essentially this means that we only see hydrogen bonds between hydrogens bound to N, O, or F (second Period electronegative elements) and N, O, or F. So we can have O-H O, O-H N, O-H F, N-H O, N-H N etc. hydrogen bonds. This is because hydrogen bonds involve dipole-dipole interactions, but they also have covalent character (about 10% of the sharing we see in true covalent bonds) which requires that the participating atoms be small enough to get close enough to allow such partial sharing. (Grp IVA-VIIA bp plot, text Fig 10.4, p 427:

Hydrogen bonding accounts for much of the special properties of water, such as its very high boiling point (261°C higher than methane with only a 10% increase in MW), high viscosity, high heat capacity etc. which in turn are due to the strong bonds between the individual molecules so they stick together.

Examples of water excluding non-polar substances to force the formation of biomembranes, separate out oils etc.

Plot of covalent hydrides in groups 4A-7A

Equilibrium Vapor Pressure

Occurs when rate of evaporation = rate of condensation. Must have some liquid (or solid for sublimation) present. (Figure 10.39, p 460)

Recall that:

Quantitative variation of vapor pressure with temperature:

Plot (Pvap vs. T; upward curve) Figure 10.42, p 462

plot of water vapor pressure vs. temperature

public domain image via Wikipedia Creative Commons


Plot (lnPvap vs 1/T; linear with negative slope, T = K) Figure 10.42, p 4462

plot of ln (vapor pressure) vs. 1/T

For the linear plot can find the equation (y = ax + b):

equation of line for plot of  ln (vapor pressure) vs. 1/T

where a = the slope = -deltaHvap/R and R = 8.315 JK-1mol-1. So

Clausius-Clapeyron equation

This expression is known as the Clausius-Clapeyron Equation.We can use this equation to find useful information such as the boiling points of liquids at different elevations (and thus pressures).

Example: Find the boiling point of water at 10,000 ft elevation if the atmospheric pressure is 508.4 mmHg. deltaHvap = 4.39 x 104 J/mol.

How do we solve this? If we take the difference between the two situations we get:

ln P1 - ln P2 = -deltaHvap/R (1/T1 - 1/T2) + b - b

reaarranging and recalling that log a - log b = loga/b

ln P1/ P2 = deltaHvap/R (1/T2 - 1/T1)


1/T2 - 1/T1 = (R/deltaHvap) (ln P1/ P2)

putting in numbers

1/T2 = (8.315 JK-1mol-1/ 4.39 x 104 J/mol) ln (760 mmHg / 508.4 mmHg) + 1/373.15 K

1/T2 = 7.62 x 10-5 + 2.68 x10-3 = 2.76 x 10-3

T2 = 362.7 K = 89.7 °C

Notice that we can also use the data from vapor pressures (or boiling points) at two pressures to calculate a value for deltaHvap!


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© R A Paselk

Last modified 22 April 2013