Please collect ONE clicker each from the front. We will use them for a review of multiple choice questions. Please return clickers at the end of the lecture. Self-Assembly: Micelles As a surfactant is added to water, the molecules adsorb at the air/liquid interface, but otherwise are free in solution. Above a certain conc., they spontaneously aggregate into micelles. This occurs at the CRITICAL MICELLE CONCENTRATION (c.m.c.) at the c.m.c. Reduced Interaction of chains with water Hydrophobic interactions between chains A “soap” solution contains both individual surfactants dispersed in water and aggregates (micelles). Thus a soap-water mixture is a suspension of micelles in water. Because the relatively large micelles scatter light (colloidal), soapy water looks cloudy. Soap Blackman Figure 22.4 Blackman Figure 22.3 Much of what we call dirt is non-polar. Grease for example consists of long chain hydrocarbons. However water, the solvent most commonly available to us is very polar and will not dissolve ‘greasy dirt’ Soap can be viewed as an emulsifying agent, since it acts to suspend the normally incompatible grease in the water. Because of this ability to assist water in ‘wetting’ and suspending nonpolar materials, soap is called a wetting agent or surfactant. Detergents Artificial soaps are known as detergents Most widely used class of detergents used are the alkylbenzene sulfonates (with –SO3- group) Fabric softener are often quaternary ammonium salts “Hard” and “Soft” Water “Hard water” contains high amounts of divalent ions such as Ca2+, Mg2+, Fe2+. The disadvantage of soaps is that the anions form precipitates with the cations like Ca2+ and Mg2+. This forms a scum and reduces the soaps’ efficiency. Ca2+ + 2 C17H35COONa(aq) → (C17H35COO)Ca (s) + 2 Na+ Lipids are broadly defined as any amphiphilic, naturallyoccurring molecules. The term is also used more specifically to refer to fatty-acids and their derivatives, as well as other fat-soluble sterol-containing metabolites such as cholesterol. fats phospholipids (with a organophosphate group) waxes steroids Hydrophobic tail Fats that are esters of glycerol are called triglycerides. Soaps are produced by saponification: the hydrolysis of lipids to glycerol and salts of fatty acids (carboxylate salts = soaps) by KOH or NaOH. Figure from Silberberg, “Chemistry”, McGraw Hill, 2006. Lipids Polar-ionic head KOH carboxylate salt glycerol Self-Assembly in Lipids In the self-assembly of surfactants and lipids, hydrophobic interactions are important Head group Tail group A lipid is an amphiphilic molecule, but rarely exists as a monomer. air water monolayer Micelle Inverse micelle (in nonpolar solvent) Lipid bilayer Phospholipids Phospatidylcholine hydrophilic Apolar hydrophobic a bilayer Long hydrophobic tails Polar head Phospholipids are similar in structure to fats in that they are esters of glycerol. However unlike fats they contain only two fatty acids. The third ester linkage involves a phosphate group, which gives phospholipids two distinct parts: long non-polar tail polar substituted phosphate “head” Phospholipids tend to form bilayers in aqueous solution with the tails in the interior and the polar heads interfacing with the polar water molecules. Self-assembly in Phospholipids Phospholipids prefer to form bilayer structures in aqueous solution because their two fatty acid chains do not pack well; Phospholipids can form either unilamellar vesicles (liposomes) or multilamellar vesicles; unilamellar vesicles (liposomes); highly stable, can be used as drug and enzyme delivery systems multilamellar vesicles McGraw Hill, 2006. Figure from Silberberg, “Chemistry”, Cell Membrane Ca. 8 nm thick A cell membrane is a bilayer of phospholipids, embedded with various proteins, and protects the cell from the extracellular fluid that surrounds it. Allows nutrients and other necessary chemicals to enter the cell and waste products to leave, through the proteins that act as pumps, gates, and channels. Biological membranes are sites of biochemical reactions that include photosynthesis, electron transfer, oxidative phosphorylation; Facilitate cell motion; provide cell recognition and cell fusion. Fluid Mosaic Model The most widely accepted model of this transfer of nutrients and waste is called the fluid mosaic mode, proposed by S. J. Singer and G. L. Nicolson, in 1972. The phospholipid bilayer is a fluid matrix: the bilayer is a twodimensional solvent, lipids and proteins can undergo rotational and lateral movement Small uncharged molecules such as water, oxygen and carbon dioxide diffuse freely through the bilayer, while other substances pass through “gates and passages” provided by specific proteins embedded in the membrane. McGraw Hill, 2006. Figure from Silberberg, “Chemistry”, CHEM1612 - Pharmacy Week 13: Review of Concepts Dr. Siegbert Schmid School of Chemistry, Rm 223 Phone: 9351 4196 E-mail: siegbert.schmid@sydney.edu.au Unless otherwise stated, all images in this file have been reproduced from: Blackman, Bottle, Schmid, Mocerino and Wille, Chemistry, John Wiley & Sons Australia, Ltd. 2008 ISBN: 9 78047081 0866 CHEM1109 – Chemistry for Life Sciences 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. Solubility Oxidation Numbers Complexes Redox Reactions Electrochemical cells Electrolysis Electrodes Chemical Kinetics Radiochemistry Colloid Chemistry 1. How did you get to Uni today? 67% 33% 0% 0% 0% 0% 1. 2. 3. 4. 5. 6. On foot By bike By public transport (train, bus, ferry) By car With my chauffeured limousine Other 2. What degree are you enrolled in? 20% 40% 20% 1. 0% 0% 0% 0% 4. 20% 8. 2. 3. 5. 6. 7. Bachelor of Science Bachelor of Medical Science Bachelor of Pharmacy Bachelor of Arts Exercise & Sports Science Bachelor of Health Science Physiotherapy Other 3. What is the expression for the solubility product constant of Ca3(PO4)2 ? 50% 50% 0% 0% 1. 2. 3. 4. Ksp = [Ca2+] [PO43-] Ksp = [3 Ca2+]3[2 PO43-]2 Ksp = [Ca2+]3[PO43-]2 Ksp = [Ca2+][PO43-] Correct 4. Which of the following statements regarding the solubility of MnS is correct? 33% 67% 1. 0% 0% 3. 0% 2. 4. 5. pH has no effect on the solubility of MnS. MnS is more soluble at pH 12 than at pH 7. MnS is more soluble at pH 4 than at pH 7. Correct The solubility of MnS does not depend on temperature. In all conditions [Mn2+] is different from [S2-]. Answer: 3 In water solution S2- is basic and takes H+ leaving OH- ions in solution. Therefore, the overall dissolution of insoluble MnS is: MnS + H2O → Mn2+ + HS- + OHAdding acid, takes away some of the OH- and moves the reaction towards the right (increasing solubility). 5. Referring to the reaction PbO (s) + CO (g) → Pb (s)+ CO2(g), which of the following statements is correct? 50% 1. 50% 2. 0% 3. 0% 4. 0% 5. Pb in PbO is oxidised by the oxygen. This is not a redox reaction. PbO is the reducing agent. CO2 is the oxidising agent. Correct Pb in PbO is reduced by the CO. 6. How is an aqueous solution affected if we dissolve in it a nitrate of a cation such as Fe3+, Cr3+ or Al3+? 50% 0% 0% 50% 0% 1. 2. 3. 4. 5. The solution is unaffected. The pH of the solution increases. These nitrates are insoluble in water. The pH of the solution decreases. Correct The nitrates form complexes with water. Answer: Acidity of Aqueous Transition Metal Ions A small and multiply-charged metal ion acts as an acid in water, i.e. the hydrated metal ion transfers an H+ ion to water. 6 bound H2O molecules 5 bound H2O molecules 1 bound OH(overall charge reduced by 1) Acidic solution 7. What is the formula of the coordination complex hexaamminecobalt(III) tetrachloroferrate(III)? 25% 25% 0% 25% 25% 1. 2. 3. 4. 5. [6Co(NH3)][4FeCl] [Co(NH3)6][FeCl4] [Co(NH3)6][FeCl4]3 [Co3(NH3)6][Fe3Cl4] [FeCl4]3 [Co(NH3)6] Correct 8. What is the missing particle for the following nuclear decay process? 14 6 50% 1. 25% 2. 0% 3. 25% 4. 0% 5. 0 1 1 0 0 1 C n 4 2 He 14 7 N? Correct 9. Which of the following statements regarding this electrochemical cell is correct? E0Zn=-0.76 V; E0Cu =0.34 V. Voltmeter Salt bridge Cu Zn Zn2+ 100% 1. 0% 2. 0% 3. 0% 4. Cu2+ Zn is oxidised at the anode and Cu is reduced at the cathode. Electrons flow from left to right. Zn is oxidised at the cathode and Cu is reduced at the anode. Electrons flow from left to right. Zn is oxidised at the anode and Cu is reduced at the cathode. Electrons flow from right to left. Zn is oxidised at the cathode and Cu is reduced at the anode. Electrons flow from right to left. Correct 10. How does temperature affect the kinetics of a reaction? 100% 1. 2. 0% 3. 0% 4. 0% 0% 5. Temperature does not affect the kinetics of most reactions. Increasing the temperature increases the reaction rate because it increases the amount of collisions occurring between reactant molecules. Increasing the temperature only increases the reaction rate of exothermic reactions. Increasing the temperature increases the reaction rate because it increases the fraction of collisions with enough energy to exceed the activation energy. Correct Increasing the temperature increases the reaction rate because it decreases the value of the activation energy. 11. Which of the following statements concerning the solubility of a mixture of NiS and CuS of equal initial concentrations is true ? (Ksp(NiS) = 1·10-22; Ksp(CuS) = 4·10-36) 0% 100% 0% 0% 0% 1. 2. 3. 4. 5. NiS will precipitate first from a mixture of the two salts. Both salts are highly soluble in water. The presence of NiS increases the solubility of CuS. It is not possible to selectively precipitate the two salts. CuS will precipitate first from a mixture of the two salts. Correct 12. Calculate the rate of production of NO2 for the reaction: 2 N2O5 → 4 NO2 + O2 knowing that the rate of consumption of N2O5 is - 5.00·10-6 M s-1. 100% 1. 0% 2. 0% 3. 0% 4. Rate of production of NO2 = 0.00001 M s-1 Rate of production of NO2 = 1.00·10-5 M s-1 Rate of production of NO2 = 20 ·10-6 M s-1 Rate of production of NO2 = 2.500·10-5 M s-1 Correct 13. Which of the following systems is an example of a sol? 0% 1. 67% 2. 0% 3. 33% 4. Mist Milk Paint Mayonnaise Correct 14. Identify the following symbol as an element and number its protons, 30 neutrons and electrons: 14 X . 1. 2. 3. 4. 5. Zn, neutrons=30, protons=14; electrons = 16 Si, neutrons=16; protons=14; electrons=14 S, neutrons=14; protons=16; electrons=16 Si, neutrons=14; protons=16; electrons=16 Zn, neutrons= 30; protons=14; electrons=14 Correct 15. What geometry and what kind of isomers does the complex [Co(NH3)4Cl2]+ have? 50%1. 50%2. 0% 3. 0% 4. Square planar geometry and no isomers. Tetrahedral geometry and one linkage isomer. Correct Octahedral geometry and two geometric isomers. Square planar geometry and two geometric isomers. Answer Summary You should now… 1. RETURN YOUR CLICKER!! 2. Revise all notes 3. Work through past exam papers 4. See Duty Tutor or myself for help (sooner rather than later) Good luck in your exams!