sare “PRINCIPLES OF PHYSICAL CHEMISTRY Gerhard Ex (1934— revolutionized surface chemistry. He provided a detiled desertion of how chemical reactions Take place on surface, thereby laying the foundations of modern sutface chemistry. Using surface study teetnigues such as LEED, he has “married together a range of techniques that let sciendss measure exactly what happens when gas molecules sick 16a soll surface”. His research has explained why the ‘ozone layer is thinning and tow fuel cells prodoce energy without pollution. [Review Questions 1. How doc cemizomiondifer from plszotion? Dias the ftors which nlence adorn of a gas ona ‘3d 2 lanes trey Lang's inlet try of son. Desve an exeson for Lama's storinn item. Shaw tht at sort press, Langmuir’ sleleelar adsorption Koterm becomes Mental wih Freedich option Sade, Discus briefly BET tery of mine asin, Deive sind Gite adsrplen tte fo the adsorption ofa soe onthe sti fa i ‘What ae surfer fins ous? Show ow te sue ln pressure varies with fli ae Describe bey the moter cigs wd fo ating sre. Il Problems 1 AL0°C apd 1am presure, the volume of aivgen gas required to form a monolayer ona sample of reo is 1555 ex of eared. Cale the sun arn per gram chteoal Aves of ers-scton of Np bobble Teed (en BS (ns 6684 2 The falioing dia were obi! on the ain sede 2d caren! {st} (ool do) 005, oo 030 10 15 2@ 201 096 on 16 os Very tht the dat obey te Fresh inter, a = Ap" where @ isthe mass adored per unt mas of cfaroa. Determine te cose Fad Tass b= O16 j= 08) 1 The densy of liquid ethane ie 0466x109, alee he approximate Grosser area of «mathe oleae TAs 1610 wl | Cafe te srice cee concenaton fr « 1.00 M aqueous sluion of NILNO sng the flowing Ex at we (wal a) on ror 200 300 10 200 @ or} 5 as | us | ma 7633 | (as Fy = 3000" wl) 45. Calle the efeive thins of he Laat Byer ia the system deste in Problem 6, (Ans. 23X10 my 6, Calcite how longa hydrogen som will remo onthe srface of 2 slid a O°C if ts desorption activation cnergy 15 150 W mot Asan tt = 10 (Ane. 39810" seco) MACROMOLECULES Macromoleesor polymers ae very high molar miss compounds consisting of sutra units inet conesed by covalent bons. Their molar mass may vary from 5,000 to several mils, The Chenisuy of tee gant molecules own a8 polymer chemistry or marcromolecar stems Furdaneatal research In polymer chemistry was dove from 1920 t0 1950 bythe Geman stems, Hermann Stange (188.1965) who wou the 1953 Chemistry Nobel Prize, Ket Zelr (898-1973), Gili Nata (1903-1979) and Paul 5 Fry (190-1985) also made sigaifeant combust he Subject. Flory was awarded te 1974 Chemistry Nobel Prize. P.G. de Genses (1922, the French physi was awarded the 1991 Phys Nobel Prize for studying polymer tiqid crys end Aeveloping the scaling concep in polymer mais. Research ia syaeic polymer chemistry has grown at huge pact. Several inusties in the USA the former Soviet Union and Japan have specialied in the sytess of high molar mass compounds Hom lw molar mas comgouns at sarting materials, Some indsties have specialized in Oe protuction of plats, syetie ber, sabe bes nequer, punts, varus, adhesives and italators, fact he pastes lady covers several vate of syateic polymers having 2 tide range of propeties. Some of them are rperor to even gold and paiaum in chemical Tessar and rcate tie mechan properies even when cooled r0 50°C and heated to +500°C. ‘he sagt of eter polymers egal ha of mals sproaching eve diamond in harness. Satie ‘nbber is speror to natural rbber in many respess. Some Yaris act as gas-inpermeable and petrol and ol-resnaat robber; oer do ao lose thc elastic properties at temperatures rangag from -80°C to +300°C. Alo sym Res are far stronger than taal fibres. These caf be Converted into eresse-proot fis and exelent arial furs. A major dsovery inthe lt 19708 tras he preparation of conducting organ polymers suchas te alogen drvatves of pojaceene tod te one-dimensional polymers, (ON), by H, Shirakawa, A, MacDiarmid and A, Heeger. These seientis were awarded the 2000 Chemistry Nobel Prize [A polyiter consists of a large number of simple monomer structural units which are cepeated ‘over and over again to form a giant molecule called a macromolecule. The simple unit is called the epeat unit. Un the polymers =--++-A—A—AAAx-Avceee and <= A=B—AB-AMBe=-, instance, the repeat units are A and A~B, respectively. The monomeric structural unit of poyetylene is ~CHy—CH—. For natural rubber, viz H-CHy-CHy-E=C CH His the pt i Fs a on 7 ‘The polymers are formed from monomes by a process analogous fo the threading of beads: Some vrsare ee PRINCIPLES OF PHYSICAL CHeNuSTRY Mace faa Polystyrene is used for making bles and jars, refrigerator linings and also films and fame. PVC isa tough and rigid material used in making phoaograph records. Plastcised PVC, obtained by the addition of appreciable amounts of low molar mass materials to PVC to increase is plasticity, 2 finds extensive use inthe manufactur of floor tes, rain coats, hand bags, upholstery, curalas, et. 2 Polystrene. This is obi A styrene This is obined by the polymeric of yren. The degree of polymerization represents the munber of structural or monomeric units cortained in a polymer. Wt is generally designed by the symbol, p. The molar mass M of the polymer aa pia i fated to p by the equation p= Mim where m isthe mola mass of monometie unt. Tus, A= CO — O i (Clasification of Polymers. During polymerization, the monomer molecules may conbiae in @ bead-to-head (4, «) and wai-to-tal (8; 9) arrangement, as showa : bie-box fier Bayo ff sop — ba ft ‘Alternatively, they may combine in a head-to-tail (a, f) arrangement, as shown eect wg BBB Bi ci t Peet . _ oo a Peli ay a psd ns nia r,s hove Foy (oath tan te mo fifty fc fice ft es te) (PMMA). This is ebisined oh ORB FCF Ci mmotueryae. The moaomer pee by the polmerzaton of mety { tt ‘scetone through the cyanohyétria reaction, Rk R R f os aie ; may be mote tat a carbon stom ofthe pyr ar asymmetric ce each of then i ci-E-ct, en 5 ; soci 0 Rind waar eto a ty me ee et fhm i ON —> cll-taen BE cid bo cays xyes ‘monomer unis which may ths have d- and -contiguaton. The seal a of te oy +, spl anaes by Mey mebacyite substituent R groups depends upon the manner in which the d~ and /-coaiguations are dstibuted sem nt acne ° Ga tty “Polymers im which all the asymmetric carbon atoms have the same (d- or /-) configuration are 2 |e i ‘led isotatic polymers. The plane representation of an iotactic polymer is ax shown below + boocn,] = ehaty tebe gad res AA semen tet a ela ioe i oe gt tine et Poe tig ns of al use Koo lac ame Sen a Te pe preen o e erai Cth cha pf hi Kyte My it HR ' hy 3 : NANNY ne me u i Polymers having regular alternation of d- and configurations in the molecular chains are caled ‘syndiotactic polymers. fo syndiotactic polymers, the substituent groups lie alternately above and : below the main chain, ax shown below : A