Chem 106 Thursday 10 Feb 2011

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1 Chem 106 Thursday 10 Feb 2011 Colligative Properties overview Vapor Pressure of Liquid - effect of non-volatile solute (Raoult) Boiling Point Elevation Freezing Point Depression Osmotic Pressure 2/10/2011 1

2 Colligative Properties Overview Colligative mean holds together. It refers to how solutes change the properties of the liquid based on the concentration of the solute (and not the shape or type). 2 nd phase (vapor, solid, or through a membrane) solution solvent solute The solute molecules or ions block the surface and prevent escape of the solvent molecules. The type of particle does not matter. 2/10/2011 2

3 Effects of non-volatile solutes: 1. Vapor pressure lowering (Raoult s Law) 2. Boiling point elevation 3. Freezing point depression 4. Osmotic pressure lowering 2/11/2009 3

4 Vapor pressure lowering by a non-volatile solute (Raoult s Law) P solution X solvent P 0 solvent vapor pressure of solution due to the solvent molecules = mole fraction of x solvent vapor pressure of the pure solvent Recall that: X solvent moles solvent total moles of solution moles solvent moles solvent moles solute 2/10/2011 4

5 X ether P X Given data ether ether P P ether 0 ether X P P ether ether 0 ether P 0 ether mmhg mmhg X ether mol ether mol ether mol Chl Given Solve for mol Chl, then convert that to grams using molar mass. Now solve for mol Chl 2/10/ X ether mol ether + X ether mol Chl mol Chl = mol ether 1 X ether X ether = mol ether

6 47.85 mol Chl mol Chl mol Chl 1 - X mol ether X g Eth ether ether mol Chl 1 mol Eth g Eth g Chl mol Chl g Chl mol Chl 2/10/2011 6

7 Effects of (non-volatile) solutes: 1. Vapor pressure lowering (Raoult s Law) 2. Boiling point elevation 3. Freezing point depression 4. Osmotic pressure lowering 2/11/2009 7

8 Colligative Properties Overview Colligative mean holds together. It refers to how solutes change the properties of the liquid based on the concentration of the solute (and not the shape or type). 2 nd phase (vapor, solid, or through membrane) solution solvent solute The solute molecules or ions block the surface and prevent escape of the solvent molecules. The type of particle does not matter. 2/11/2009 8

9 2/10/2011 9

10 Boiling point elevation by non-volatile solute Example: anti-freeze prevents boilover (and freezing) of engine coolant. H H O H O H H H ethylene glycol (toxic) H O O H H C H 3 H H propylene glycol These compounds are used because they are very soluble in water, non-corrosive to metal parts, and relatively inexpensive. 2/11/

11 Phase diagram of water 1.00 Vapor pressure of solution at T = 100 C is LESS THAN vapor pressure of pure water. Solutions still require P = 1.00 atm to boil. P (atm) T ( C) 2/11/ So, to get the solution to boil, you have to heat it hotter.

12 Boiling elevation = ΔT bp ΔT bp = K bp m solute molal boiling point elevation constant 2/11/

13 Boiling point elevation by ionic compounds: The colligative effect depends on the NUMBER OF PARTICLES ONLY. So we take this into account by including the factor i. i = moles of particle per mole of solute These can be molecules, or separate ions of ionic solute. i = 2 for NaCl = 3 for CaCl 2 = 3 for H 2 SO 4 = 1 for ethylene glycol ΔT bp = ik bp m solute 2/11/

14 2/11/

15 C D B A mol AlCl 3 4 mol ions mol ions x kg mol AlCl kg mol CaBr 2 3 mol ions mol ions x kg mol CaBr kg mol Al ( NO 3 ) 3 4 mol ions mol ions x kg mol Al ( NO ) kg mol gluc 1 mol molec mol molec x kg mol gluc kg /11/

16 Which aqueous solution (each 0.50 m) has the highest boiling point? 1. Ethylene glycol 2. Chromium (III) nitrite 3. Sodium chloride 4. Calcium sulfite Ethylene glycol Chromium (III) nitrite Sodium chloride Calcium sulfite 2/11/

17 Which aqueous solution (each 0.50 m) has the highest boiling point? 1. Ethylene glycol I = 1 2. Chromium (III) nitrite Cr(NO 2 ) 3 i = 4 3. Sodium chlorate NaClO 3 i = 2 4. Calcium sulfite CaSO 3 i = 2 (Please review ion charge, name, and formula.) 2/11/

18 Effects of (non-volatile) solutes: 1. Vapor pressure lowering (Raoult s Law) 2. Boiling point elevation 3. Freezing point depression 4. Osmotic pressure lowering 2/11/

19 Solute molecules or ions BLOCK access to the solid surface 2/11/

20 Phase diagram of water & solutions melting point depression Must cool to -4 C (or whatever) to get ice again. Pure water + C/1 atm Solution (no C/1 atm 1.00 P (atm) New triple temp/pressure 0.0 T ( C) -> 2/11/

21 Phase diagram of water and solutions melting point depression Liquid phase for pure liquid Liquid phase for solution 1.00 P (atm) 0.0 T ( C) -> 2/11/

22 2/11/

23 Ice crystals in seawater are nearly fresh. 2/11/

24 Ice metamorphoses over a period of weeks and months, which eliminates salt impurities within the crystals. 2/11/

25 Arctic explorers say that one-year ice is good for nothing, two-year ice is OK to cook with and only three-year ice will do for tea. 2/11/

26 Freezing Point depression elevation = ΔT fp ΔT fp = K fp m solute molal freezing point depression constant 2/11/

27 Melting point depression by ionic compounds: The colligative effect depends on the NUMBER OF PARTICLES ONLY. So we take this into account by including the factor i. i = moles of particle per mole of solute These can be molecules, or separate ions of ionic solute. i = 2 for CsI = 2 for HCl = 3 for Ca(ClO 4 ) 2 = 1 for sucrose ΔT fp = ik fp m solute 2/11/

28 Which aqueous solution (each 0.50 m) has the lowest freezing point? 1. Sodium bromide Sodium chlorate 3. Calcium chlorate 4. Cobalt (III) nitrate Sodium bromide Sodium chlorate Calcium chlorate Cobalt (III) nitrate 2/11/

29 Which aqueous solution (each 0.50 m) has the lowest freezing point? 1. Sodium bromide NaBr i = 2 2. Sodium chlorate NaClO 3 i = 2 3. Calcium chlorate Ca(ClO 3 ) 2 i = 3 4. Cobalt (III) nitrate Co(NO 3 ) 3 i = 4 2/11/

30 g/mol T m m x fp solute K fp m T fp K fp T K 2/11/ solute o fp solute o m solute fp mol solute kg solvent mol solute kg solvent C C / m kg H O m x 1 kg H 2 O g H O g H O 2 i = g g M g / mol g / mol mol mol 2 mol

31 Which one of the following is the most reasonable formula for this compound? 1. C 5 H 2 2. C 4 H C 3 H 6 O 4. C 3 H 8 O Not enough H s Too many H s C 2 H 6 O 2 Formula wrong for 62 g/mol C5H2 C4H14 C3H6O C3H8O 2/10/

32 This is the formula for ethylene glycol, which is possible to synthesize by rather easy methods in the lab, in contrast to the molecule shown below. 3. C 3 H 6 O C 2 H 6 O 2 Turns out that C 5 H 2 does have at least one energy minimum as calculated by the PM3 semi-empirical method. This molecule might exist in the gas phase at close to Absolute Zero out in space somewhere 2/10/

33 Effects of (non-volatile) solutes: 1. Vapor pressure lowering (Raoult s Law) 2. Boiling point elevation 3. Freezing point depression 4. Osmotic pressure lowering 2/11/

34 Osmotic pressure = extra pressure that must be applied to the SOLUTION SIDE of semi-permeable membrane to EQUALIZE solvent flow. 2/11/ OSMOSIS = diffusion through a semi-permeable membrane.

35 OSMOTIC Pressure = (atm) = im solute RT i = Moles of particles per mole of solute Molarity of solute Absolute Temperature (Kelvin, K) Gas Constant = L-atm/(K-mol) 2/11/

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