$AS3120 Physical and Organic Chemical Testing Technique Lectver Wace Ng Prepared by KW Lau Moe by Walace Na Ch Physical Characterization and Separation Techniques Paraars4 Content: Introduction Melting and boiling points Refractive index (1/5!) Liquid-liquid extraction - Partition coefficients( ABC 82) 5, References 6. Tutorial ens Acsnaprae Sor ct igre eae tone Mm CeO at Bosman? Dense se rood sea Introduction 1. Physical characterization techniques = Determination ofthe physical properties e.g. boling point (bp), metting point (mp), solubity of substance ~ Characterization: to identily the substance based an the physical property. = Common physical characterization techniques 8 expt2 ture Ne expts Lecture Refine index RAR) Expt2———Leete PattoncooideniSHEBM) Expt Leche 1.2. Physical separation techniques 4 ‘Separation of a mixture of components based on the ciferences in physical properties Liquid exacton ung separating nn! Sonmeecn (REAR) soniye? Lb Reoysalizaton Sobtily —Exté Lab ‘Sipe an ta disiaton (Bp egt2 ab ame) Ents Ets Sarg out rpaneconpounds Sokbily Gxt Lab auersiee) Dyjingompriccompaunds Sokbiy Expt Lab Eats2. Melting and boiling points 2.4, Melting point (mp) « the temperature at which it changes state from solid to liquid. + At the mp - the solid and liquid phase exist in equilibrium, + MP depends on pressure and is usually specified at a standard pressure such as 1 atmosphere or 400 kPa, + Freezing point- the temperature change from liquid to solid 2.1.4 Factors affecting mp 2.1.1.4 Inter Molecular Forces Higher intermolecular forces, higher mp Covalent compounds are weaker compared with the onic ‘compounds and the former has lower mp 2.1.1.2. Shape of Molecules packed in a regular pattern, the substance has a higher ‘melting point than a substance that with oddly shaped ‘molecules which do net let the substance to have a well packed molecules (good contact with each other 2.1.1.3 Size of Molecules The substance with smaller molecules melt at lower temperatures than the substances with larger molecules. 7 2.1.2, Mp and bp of some chemicals, ‘Chemical mp (°C) Water 0 Tr 1668 lau 7064 Hg. -39) Pb. 327 2.2. Boiling point «the temperature at which the vapor pressure of a lauid equals the pressure surrounding the liquid and the iquid changes into a vapor. + bp depends on the surrounding environmental pressure. + Aliguid in partial vacuum has @ lower boling point than when that Iquid is at atmospheric pressure.+ For example, water bols at 100 °C at sea level, but at 93.4 °C. at 1,905 m altitude, 2.2.1 Factors affecting bp 2244 > The relative strength ofthe 4 intermolecular forces is + Tonic > Hydrogen bonding > dipole dipole > Van der Waals 22.12- Bolling points increase as the numiber of Cs increased fora given functional group. Van der Waals (London dispersion) forces (VDWF(LD), hich are proportional to surface area (SA (London dispersion) forces. perc) [- Cao Stet =) Kat Mca we a2 [re eo °C) a 158, ] Sree Ao | ee Fe Uaauezaal Una 50) Ss hi Eo ° 10 2243, 2.3. mp and bp determination Branching decreases boling point. ‘SA decrease for branching and so does the VDWF(LD) The more sphere lke the molecule, the lower its surface area vill be and the fewer intermolecular VDWF wil operate. (Bee | per ee ere [8 je 7 i + Similar observation for molecules with H-bonding +The -OH of 1-pentanol is more “exposed” than + the OH group in 3-pentanol (which i flanked (124%... €9 ‘l)by two bulky (3A)alky groups), + so 1-pentanol will be better able to bveroaen bond, ' 2.3.1. Electrical mp determination apparatus 2camp Seth sarng (Nata) tomp ofthe mp apparatus tsuaiy 1020 bee the pected tp Set eating rate og. 810° + Raportemp rong rake tn temp forthe sample apoear to meltand | then temp or complete mling + Note: + The narrower the temp range, the higher the purity Impurity —lower the mp and higher temp range Impurity weaken the intermolecular forces as it disrupt the crystalline lattice. Mp determination ~ identification of unknown ‘sample by matching temp with standard. 3 Fil the capillary tube with 0.3-0.5 mm powder 7 2.4. Application of mp determination + By the fact that diferent chemicals have different ‘melting point, melting point determination can help to identify an unknown chemical compound + e.g, DNP test - Determination of ketones and aldehyde by 2,4-Dinitrophenylhydrazine( 2,4-DNPH) i. ms oy ha 14 2,4-DNPH reacts with ketones or aldehyde to form hydrazones. Different hydrazones(derivatized from different ketones/aldehydes) have different mp point By determining the mp of such hydrazones(after recrystallization), the unknow ketones/aldehyde can be identified 18 (Our Expt 6- Preparation of aspirin (5 > Infomation corr + Aspirin ~ mp =135 °C (note: it normally decomposé at ~10 and so the true mp may notbe obtained + Setstaring temp 105°C 2.3.2. bp determination by simple distillation method YouTube video - Determination ofthe Melting and Boiling Points of Compounds (bp determination by simple distilation method) (6.44 min) num nitibe coma epniNDOr She 16ur Expt 2- Simple distillation’ * Boling point —asds bots and he temp becomes ses) + Boling pit range — tomp at rich ho Collet istia in ‘ameesurng cylinder 3. Refractive index (RI) 18%) 3.4. Basics Physical property bike melting point, boing point + Measure of the bending of a ray of light when passing from ‘one medium inte anether. + Very sensitive tothe purity of the sample. + Depends on the wavelength (38) of the light and temperature. + Normally use yellow sodium wavelength of (0-589. nm) + Iftemp is not at T= 20°C, Rlis calculated by yt red + (T-20) x 0.00045, 18 3.2 Ri measurement + Rilke mp which can be used to identi the unknown by ‘matching the RI of sample with appropriate standards. Under standard conestion af 20°C and 589.0 nm light. + Water = 1.333 + Acetone = 1.3592 + Ethanol = 1.3591 + Acetic acid = 1.3577 + Chloraform = 1.442 Olive oil= 1.47 Glass = 1.5168 3.3, Kruss DR201.95 Digital handheld refractometer 3.3.1. Operation procedure 3.3.1.1, Calibration of the refractomer sing DI water at standard conaiton of 206 Press totum on the instrument. Check the corect scale use, 8 or BRD (for sugar content measurement) by pressing the key 3) Use aplastic dropper toad 1-2 drops of Di water tothe prism. Pros key for 3s. When calibration is complete (lakes 22s), ‘ and message willbe displayes Press to show the cairated RI value by water 20 4 53.3.1.2, Sample measurement 1) Clean the prism by gently wiping with lens paper and water (for water soluble sample) 2) Use a plastic dropper to add 1-2 drops of sample to the prism. 3) Press to display RI ofthe sample. Note: + This retractometeris equipped with an automatic temperature ‘compensation (ATC) + Than correct automatically for differences in the temp of the ‘sample to the standard temp of 20°C. 7 4. Liquid-liquid extraction(# 814218) 4.1. Basics To separate compounds based on their relative solubilities in2 different immiscible (AGATE 245) iquids, usually water (polar) and an organic solvent (non-polar). There is a net transfer of one or more species from one liquid into another liquid phase, generally from aqueous to organic. ‘Commonly performed using a separating funnel 2 Miscibilty Solvents that are miscible with water: ‘Methanol, Ethanol, 1-propanol, 2-propanol, acetone, acetonitrile, tetrahydrofuran(TFH) ‘Solvents that are immiscible with water: Chloroform, dichloromethane, ethy! acetate, diethy! ethe benzene, 1-butanol, pentane, hexane, heptane, toluene 23 be 2 byes 24+ When a solute (e.g. A) is dissolved in a system with 2 immiscible (F&EGESE)solvents, it will distribute itself between both solvents and establish an equilibrium( 4%). Yeas tee) 25 +The ratio of te concentration of solute A at ‘equllrium in solvents 1 and 2 called the Partition coefficient + Kl the pation cooeent | 1 Chis the concentaton of sokae Ain solvent 2 aS fefeter (cj ofbcanedoe aan water and ory etnor i “The process Sekar ae K HO.O(CH),C0.H yn) HOLO(CH,C0M ja As, + Solvent = water + Solvent 2= det ether 1 SoltaA= butanecoe acl + Kd- a comparison of the solubilities of the solute in these 2 solvents. + Usually, 4 solvent is water or aqueous and the other is water immiscible solvent (organic) + Ky depends on temp. + The solute is of the same molecular form in each solvent. + Most organic compounds are more soluble in organic solvents, while some organic compounds are more soluble in water, + Applications of liquid-liquid extraction + To separate a substance selectively from a mixture + Toremove unwanted impurities from a solution 4.3, Liguid-liquid extraction is more efficient in small portions of solvent instead of a single extraction with a volume of solvent equal to the sum of the small portions. 4.3.1. Explanation with an istrative example + Kyof butanoic acid [BA) (CH,CH,CH,COOH) between city! ether and water at 8 °C is 35, + Caleulate the amount of 8A extracted by shaking 100 ml of water containing 10 of bulanoic acid with 100 mL of ether. Caleulate the amount of 8A removed in each of urther ‘aractons using 100 ml of ether each time. + Compare the total amount of BA extracted in these 3 successive extractions (100 mLx 3= 300 ml) wit that in a Single extraction using 300 ml of ether ooSolution: 4 extraction Let x'be the mass of acid extracted by 100 mL of ether. Cone. of BAin ether = x/ 100 (g/mL) Cone. of BAIn water = (10-x)/ 100 (gil) [ramnicasa tno x1100 (i023 7700 35 x1 (102) =35. X=Z78.00fBA inthe fist 100 mL ether extraction 26 ‘The amount of BA left in the water after the frst ether extraction| 107.78 22.224 204 extraction Loty be the mass of acid extracted by 100 mL of ether Cone, af BAin ether = 100 (g/mL) Cone. of BAin water = (2.22-)) 100 (gimL) 1100. [amano | (222-7100 Titans y/(2.22-y) y= LTB g0f BA inthe 2 100 mL ether extraction 30 ‘The amount of BA eft in the water after the 2° ether extraction] 224.73 499 3 extraction ‘Lotz be the mass of acid extracted by 100 mL of ether Cone. af Bin ether = 2/100 (gimL) Cone. of Bin water = (0.49-2)/ 100 (gimL) 21100 ee TTIOT 21 (0.49.2) =3.5 250.3801 BA in the 3% 100 mL ether extracton 3t Hence, the otal amount of BA extracted using 3 separate tions of 100 mL of ether 7.784 1.73 + 0.38) 9 ies eat al the BA's extracted and only 10-9,89 = 0.11 9 of BA eftin the water layer) Fora single extraction using 300 mL ether + Letwg be the amount of BA extracted by 1 portion of £300 ml ether Cone. of BAin ether = w 1300 (gfmL) Cone. of BA.n water = (10-1) / 100 (g/mL) (w800) 1{(10 ~ v100} i.e. 9.13 9 of BAis extracted using one portion of 300 mL. ether + Less efficient 32Tehama pn Si puna hs Fa, Successive entacion 4.3.2. General equation eA maser A [Gore tana wate Byer ja [eecan ata eter fp [recon fan oman ner | Mass orA water yer Fraction ofA that remains in water layer of volume V, of ‘organic solvent in each extraction Is = ep e.g. based on the previous calculation of BA after 3 portions ‘of 100 ml ether extraction, the amount of BA lft in water layer is 20.011, le, 0.011 x 10.9 = 0.11a of BAleftin the water layer (P.23} 35 5. Soxhlet Extraction + Soxhlet extraction techniques are usualy used in Analytica laooratory + Used for solid materia(sample) + Soliiqud extraction ‘Apparatus needed for Soxhlet extraction: “Thimble: A cellulase-based tube (to contain slid sample} Soxhlet extractor Condenser Roun or flat bottom flask Heater Hotplate, water bath)Tre hoses wired cvs tnaalaaSosne chan Penile ‘The solvents bolted ina round bottom flask The vapour ofthe solvent reach the condenser The condensate drop int the soxhlet extractor ‘The sample is immersed in the condensate and the target compound is extracted 5. Condensate accumulates in the extractor unl tis almost full ‘The condensate flow back tthe round Bottom flask by sipron(31 2) ‘This process repeat many times unt all re compound is extracted {rom the material 37 38 ‘Selection of solvent for Soxhlet Extraction Liquid Extraction + Tho solvent must be able to dissolve target compounds isn Easton nth We mf Slvr Real Mere Efeeve Than + The solvent should not aissolve the sample material ‘ne Sarason wn nL? + The solvent should have lower boiling point than the target ‘nee an eta noaaectresclnorasicumeneactns compounds ‘5.2 Step-by-Step Procedures for Boiling Point Determination rangle: fina Testu MehalsOSioh Mscelonecs Teenie To determine the total fat in mest, ether can be used becouse: ‘isp Prose tli Post Ostemiaton 5.3 Kruss DR201-95 Retractometer “Fat is soluble in ether tps sav kuoss comlenproduteratactometerslr10"-5087201-96- “Ether does not dissolve meat protain 01-35, “Ether has low boing poit{-50-80C) 5.4. K Denniston, J. Topping and D. Q. Dorr, General, Organic, and Biochemistry, 10th ed., McGraw Hil 2020. 39 405.5. YouTube videos + Separating Components of a Mixture by Extraction (10.08 rin) https /mww youtube, comvatch?v=N96JaRnE7n0 + russ OR 201-95 Refractometers (3:40 min) hitosy/wva.youtube,comivatchv=VI5tSvwr6bU + Stuart SMP30 melting point electrical apparatus (2:34 min) hitos:/iwwn.youtube,comvatchv=2akpGQiYd08t=828 + Sealing melting point tube (1:53 min) hpsi/iwwa.youtube.comvatchv=sh-96_ Kfeg¥ + Determination of the Melting and Boling Points of Compounds (bp determination by simple distillation ‘method (5.44 min) hntps/wvw.youtube,comvatch?v=pDmWDOr_3HO at a Antena ee * 6. 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