Table of Content
Experiments
11. zeltilerin Hazrlanmas 12. znrlk ve znrl Etkileyen Faktrler 13. Donma Noktas Alalmasndan Molekl Ktlesi Tayini 14. Kinetic Study of the Reaction Between Ferric and Iodine Ions . 15. Le Chatelier Kural . 16. Asit Baz Titrasyonu 17. pH ve ndikatrler . 18. Oxidation-Reduction Electron Transfer Reactions 19. The Solubility Product Constant of Calcium lodate, Ca(IO3)2 . 20. Sabun References 50 54 57 62 66 68 71 74 82 89 92
11
zeltilerin Hazrlanmas
AMA
Deriim birimlerini renip farkl deriimde zeltileri hazrlamak.
TEORK BLG
ki veya daha fazla bileenin homojen karmna zelti ad verilir. zeltiler, kat, sv veya gaz olabilir. Bileenlerden, genellikle nicelii ok olana zc, dierine znen ad verilir. zeltinin birim hacminde veya zcnn birim ktlesinde znen madde miktarna deriim
(konsantrasyon) denir. Deriimin yksek olduu zeltilere deriik zelti, dk olduu zeltilere ise seyreltik zelti ad verilir. Belli bir scaklkta zebilecegi en fazla maddeyi zm olan zelti doymu zeltidir. Ayn maddeden bir miktar daha zebilecek durumda olan zelti ise seyreltik zeltidir. Doymu bir zeltinin deriimi yani znrlk, zcnn yapsna,
znenin yapsna, scakla ve basnca baldr. zelti hazrlarken damtk su kullanlmal, kaplarn temiz olmasna dikkat edilmelidir.
Deriim Birimleri
Molarite (M): Bir litre zeltide znm maddenin mol saysdr. 0.1 M NaOH zeltisinde 0.1 mol NaOH var demektir. Molalite (m): 1000 g zcde znm maddenin mol saysdr. 1 m HCl zeltisi, 1000 g zcde znm 1 mol HCl (36.5 g) ierir. Normalite (N): Bir litre zeltide znen maddenin edeer ktle saysdr. N= Ykseltgenme says x M Mol Kesri (X): zeltideki A bileeninin mol kesri (XA), A bileeninin mol saysnn toplam mol saysna orandr. Bir zeltideki bileenlerin toplam bire eittir. XA = na / nT nT = nA + nB + XA + XB + = 1
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Ktle Yzdesi: Bir zeltide, bir bileenin ktle yzdesi o bileenin ktlesinin toplam zelti ktlesine orannn yz katdr. %10'luk sulu NaOH zeltisi, 10 g NaOH zeltisi ve 90 g su ierir. Az miktardaki (eser miktar) konsantrasyonlar: Genellikle aada verilen birimlerden birisiyle ifade edilir. a) b) c) Binde bir ksm (Ing. parts per thousand, ppt, ) Milyonda bir ksm (Ing. parts per million, ppm, Milyarda bir ksm (Ing. parts per billion, ppb) )
znen (g) 3 ppt (ktle / hacim) = x 10 rnek (mL) znen (g) 6 ppm (ktle / hacim) = x 10 rnek (mL) znen (g) 9 ppb (ktle / hacim) = x 10 rnek (mL)
znen (g) 6 ppm (ktle / ktle) = x 10 rnek (g) znen (g) 9 ppb (ktle / ktle) = x 10 rnek (g)
rnek: 2.6 g Bitki dokusu rnei analiz edildiinde 3.6 g inko ierdii bulunmutur. Bitkideki inkonun ppm ve ppb cinsinden konsantrasyonu nedir? zm:
3.6 g / 2.6 g = 1.4 g / g = 1.4 ppm 3.6 x 103 ng / 2.6 g = 1.4 x 103 ng/g = 1400 ppb
rnek: 25 L Serum rnei analiz edildiinde 26.7 g glikoz ierdii bulunmutur. Serum rneinde bulunan glikozun ppm ve mg/dL cinsinden konsantrasyonu nedir? zm:
25 L 1 mL = 2.50 10- 2 mL 1000 L 1g 106 g
= 2.67 10 5 g
26.7 g
ppm =
mg/dL =
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n1 = n2
M1V1 = M2V2
eitlii geerlidir.
Eitlikte 1 indisi deriik zeltiyi, 2 indisi ise hazrlanmak istenen zeltiyi gstermektedir. Deriik zeltiden belirli deriimde daha seyreltik bir zelti hazrlarken nce ka mol gerektii hesaplanr. Bunun ne kadar hacimde bulunaca da nceden bilinir ve yukardaki eitlik kullanlarak deriimi belli ana zeltiden alnacak miktar hesaplanr. Bulunan miktar uygun bir l kabyla bir balon jojeye alnr ve zeri zc ile belirli hacime tamamlanr. Hazrlanan zeltiler saklama ielerine aktarlarak zerine deriimi ve hazrlanma tarihi yazlr.
DKKAT: H2SO4 zeltisi hazrlarken asit zerine su koymaynz. Patlama olabilir. Daima zeltiyi hazrlayacanz kabn dibine zelti hacminin yars kadar su koyup H2SO4 i yava yava zeltiyi srekli kartrarak ekleyiniz.
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Balon jojeye 1 L damtk su koyup zerine 11 mL %96'lk H2SO4 zeltisinden yava yava kartrarak ilave edilir. Hacim izgisine kadar damtk su ile 2 L'ye tamamlanr. 2. 3. 4. 500 mL, 0.050 M NH4OH zeltisini, NH3'n %27'lik sulu zeltisinden hazrlaynz (d=0.90 g/mL) (NH4OH amonyan sulu zeltisidir). 0,1 N, 500 mL asetik asit zeltisini laboratuvarnzda bulunan asetik asidi kullanarak hazrlaynz. 5 ppm Na2CO3, 10 ppb MgSO4, 15 ppt NaCl zeltilerinin her birinden 50 mL hazrlaynz.
SORULAR
1. 2. Ykseltgenme says ve edeer ktle nedir? Nasl hesaplanr? Neden H2SO4'in zerine su konulmaz? Aklaynz. Bu durum sadece H2SO4 iin mi geerlidir? Dier asitlerin zerine su ilave edebilir miyiz?
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12
AMA
znrlk, znrl etkileyen faktrler ve znme hzlarn incelemek. Bir zcnn (sv) kaynama scaklna uucu olmayan bir katnn etkisini aratrmak.
TEORK BLG
Bir nceki deneyden hatrlayacanz gibi zeltinin birim hacminde veya zcnn birim ktlesinde znen madde miktarna deriim (konsantrasyon) denir. Deriimi dk olan zeltilere seyreltik zelti, yksek olan zeltilere ise deriik zelti denir. Belli bir scaklk ve basnta bir znenin bir zc iinde en ok znebildii deriime ise znrlk denir. ou maddelerin verilen bir zc iinde znrlkleri azdr. zeltinin, znen ile doygunlua ulat deriim znrle karlk gelir. Baz maddeler birbirleriyle her oranda karabilirler. Tam olarak karabilen gaz zeltileriyle beraber baz sv-sv, sv-kat ve katkat madde iftlerini de rnek olarak verebiliriz. znrlk, a) zcnn yapsna, b) znenin yapsna, c) scakla ve d) basnca baldr. Bir katnn svdaki znrl yalnz scaklkla deiir. Scaklk art genellikle katnn svdaki znrln de artrr. Sv ve kat maddelerin svlardaki znrlne basncn etkisi ok azdr. Bir gazn svdaki znrl, scaklk ve znen gazn basncna baml olarak deiir. Genellikle gazlarn sudaki znrl, zeltinin scakl arttka azalr. rnein, snan sudan hava kabarcklarnn kmas. Basncn ykselme ve dmesinden sv iindeki gazn znrl ok etkilenir. Gazn basnc arttka svdaki znrl de artar. rnein, gazozlar yksek basn altnda ekerli suda znm fazla miktarda CO2 gaz ierirler. ienin kapa alp basn atmosfer basncna eitlenince artk fazla znmeyen CO2 gaz kabarcklar halinde gazozdan ayrlr.
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55
DENEY VERLER
1. a) Deneyden elde ettiiniz verileri kullanarak aadaki tabloyu doldurunuz. Kullandnz maddelerin znrln zc ve znen ynnden inceleyiniz.
zc znen eker Sodyum slfat Sodyum klorr Parafin yot Su Alkol Karbontetraklorr
b) Alkol-su ve eter-su deney sonularn karlatrnz. 2. 3. Toz haldeki kat ile kristal haldeki katnn sudaki znme hzn karlatrnz. a) Sodyum asetatn m yoksa sodyum klorrn m znrl scaklk arttka artar? Nedeniyle beraber aklaynz. b) Potasyum nitratn sudaki znrln scakla kar grafie geiriniz. c) Uucu olmayan bir katnn, zcnn kaynama noktas zerine etkisini aratrnz.
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13
AMA
Donma noktas tayini ve zcnn donma noktasndaki dme ile znenin molekl ktlesini bulmak. Kkrdn molekl ktlesini, naftalinin donma noktasndaki d kullanarak belirlemek.
TEORK BLG
Saf kat bir madde stldnda, maddenin scakl artar ve bu art erime noktasna kadar devam eder. Kat madde erirken, s katnn erimesi iin kullanldndan, scaklk sabit kalr. Katnn tamamnn svya dnmesinden sonra scaklk tekrar artmaya balar. Fakat kat ve sv halin scaklnn art hz, deiiktir. nk kat ve svnn s kapasiteleri farkldr. Aadaki scaklk-zaman grafiinden de grld gibi T1 scaklnda sv katya dnmeye balar ve bu dnm boyunca scaklk sabit kalr (t1'den t2'ye kadar). Donma sresince, paracklar sv halden kat hale geerken belirli bir geometrik ekle girer ve maddenin potansiyel enerjisi dmeye balar. Bu nedenle donma srasnda kat paracklarn oluturur karlar. ve oluumu oluan Sonuta s bu enerjisi enerji, donma
Scaklk T2 s sk k
T1
souma ile yok edilen s enerjisini tamamlanncaya kadar scaklk sabit kalr. Bu durum, deneydeki naftalinin donma noktasnn belirlenmesinde bize yardmc olur.
t0
t1
t2
Zaman
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Bir maddenin kat ve svsnn dengede bulunduu scakla maddenin erime noktas denir. rnein 1 atm basnta buz 0C'de erir. Kat erirken dzenli ve belli bir kristal yapdan dzensiz ve dank sv hale dnr. Bir mol katy eritmek iin gerekli olan s miktarna molar erime ss denir. Erime noktasndan sonra verilen s sv molekllerinin ortalama kinetik enerjisini arttracak ve svnn scakl ykselecektir. Bu durum kaynama noktasna kadar devam eder ve kaynama noktasnda durur. nk kaynama noktasnda verilen s svnn scakln ykseltmek yerine kaynama ilemi iin harcanr. Bir svnn buhar basncnn atmosfer basncna eit olduu scakla
ss ad verilir. Maddelerin stlrken zamanla scaklk deiimini veren eriye snma erisi,
maddelerin soutulurken zamanla scaklk deiimini veren eriye de souma erisi ad verilir. Gazn svya dnt scaklk (younlama scakl) ile svnn gaza dnt scaklk (kaynama noktas) ayndr. Benzer durumda, svnn katya dnt scaklk (donma noktas) ile katnn svya dnt scaklk (erime noktas) ayndr. Genel olarak bir znen madde ilavesi, zcnn kaynama noktasn ykseltirken donma noktasn ise drr. Verilen bir zc iin donma noktasnn alalmas zc iinde, znen olarak bulunan taneciklerin deriimi ile doru orantldr.
T = K d m T = Donma noktasi alalmasi K d = Donma noktasi alalma sabiti m = zeltinin molalitesi
Donma noktasnn alalmas ile ilgili lmeler, kaynama noktas ykselmesinde olduu gibi, znm maddelerin molekl arlklarnn saptanmasnda kullanlabilir. Donma noktas alalma sabiti bilinen belli miktarda bir zc iinde, molekl arl bilinmeyen bir madde bir miktar tartlarak zlr. zeltinin donma noktas saptanr. zeltinin donma noktas alalmas ve molalitesi hesaplanr. Bu deneyde zc naftalin, znen madde ise kkrttr. Kkrdn bir mol, 1000 gram naftalinde zndnde zcnn donma noktasn 6.9C drr (Kd = 6.9C/molal). Bilinen bir ktledeki naftalin iinde, yine bilinen bir ktledeki kkrd zerek donma noktasndaki d llecek ve bylece kkrdn molekl ktlesi bulunacaktr.
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DENEYN YAPILII
Aadaki ekilde gsterilen dzenei kurun. Termometreyi iki delikli mantar tpaya
yerletirirken, termometreyi ve tpay havlu ile sarn ve yava yava dndrerek deliin iine termometre skalasnn 70C'den yukars grlecek ekilde tpn dibine demeden yerletirin (aksi durumda termometreyi krabilirsiniz). 5 g Naftalin tartn ve lm deerini m2 zcnn ktlesi olarak kayt edin. Tp doldurmadan nce temiz ve kuru olmasna dikkat edin. Naftalinin tamamn byk bir deney tpnn dip ksmna gelecek ekilde boaltn. Termometre ve tel kartrcy yerletirdiiniz tpayla, tpn azn kapatn ve tp, iinde su bulunan bir beherin iine yerletirin. Naftalinin tamam eriyinceye kadar su dolu beheri yava yava stn. Erime noktas 80C civarnda gzlenmelidir. Beherin altndan beki aln ve kapatn. Srekli kartrarak her 30 saniyede bir scaklk okumalarn kayt edin. Bu ileme scaklk 75C'ye dnceye kadar devam edin. 1 g Kkrt tartp (tartm deerini m1 znenin ktlesi olarak not edin) souyup katlam olan naftalinin zerine ekleyin. Termometre ve kartrcy yerletirdikten sonra naftalin ve kkrdn tamam eriyinceye kadar su banyosunda stn. Beki sndrdkten sonra 85-70C aralndaki scaklk dmesini her 30 saniyede bir kayt edin. Deneyiniz tamamlanmtr. Deney verilerinizi kullanarak hesaplamalar yapnz.
Kartrc Termometre
Deney tpn temizlemek iin iindekiler eriyinceye kadar su banyosunda tekrar stn. Tpn iindekiler tamamen eridikten sonra termometre ve kartrcy karn. Sonra erimi naftalini atk naftalin etiketi yaptnlm olan behere boaltn. Erimi naftalini asla lavaboya dkmeyin.
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Naftalinin (zcnn) ktlesi (m2) Saf naftalin iin souma erisinin verileri: t (zaman, s) T (scaklk, C) Kkrdn (znen) ktlesi (m1)
t (zaman, s)
T (scaklk, C)
T (scaklk, C)
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T (C)
T (C)
t (s)
t (s)
2.
Souma erilerinden donma noktalarn belirleyin. Saf naftalinin donma noktas (T1) zeltinin donma noktas (T2)
3.
Naftalinin Kd deeri 6.9C/molal'dr. zeltinin molalitesini hesaplayn. Donma noktasndaki dme (T) zeltinin molalitesi (m)
4.
Molalite (m), m1 ve m2 verilerini kullanarak kkrdn molekl ktlesini hesaplayn. Kkrdn molekl ktlesi (M)
5.
Kkrdn atomik ktlesi 32 g/mol'dr. Bulduunuz molekl ktle deerini kullanarak kkrdn molekl formln Sn olarak yazn. n
6.
Kitabnzdan kkrdn gerek molekler formlne bakn. Kkrdn teorik molekler ktlesini ve deneyinizdeki hata yzdesini hesaplayn. M deki hata yzdesi
SORULAR
1. 2. Naftalinin donma noktas deerindeki hata yzdesi nedir? Kkrdn molekl ktlesini tayin ederken naftalin iin kendi bulduunuz donma noktas deerini kullanmann avantaj ne olabilir?
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14
OBJECTIVE
Purpose of this experiment is to study the kinetics of the oxidation reduction reaction between ferric (Fe3+) and iodide (I-) ions i.e.; to determine order of the reaction with respect to both ions. 2Fe3+ + 3I- = 2Fe2+ + I3Rate expression for this reaction is
d [I3 ] 1 d [Fe 3 + ] = = k [Fe 3 + ] a [I - ] b 2 dt dt
Rate =
THEORY
Parts A and B of this experiment are concerned with the evaluation of exponents a and b, respectively, in the rate expression. The initial rate is determined by measuring the time in seconds required for 4x10-5 mole of Fe3+ to be reduced to Fe2+. This is indicated by adding starch solution and a small, constant amount of S2O32- to each mixture. The following reactions then occur: 2Fe3+ + 3I- = 2Fe2+ + I3I3- + 2S2O32- = 3I- + S4O62slow fast
As soon as the S2O32- has been consumed, any additional I3- formed by the reaction between ferric and iodide ions will react with starch to form a characteristic blue color. Note that when the blue color first appears, the decrease in the concentration of Fe3+ from its initial value is just equal to initial concentration of S2O32- in the mixture. Thus,
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Initial Rate =
1 d [Fe 3 + ] 1 d [S 2O 3 ] i = 2 dt 2 t
where [S2O32-]i is the initial concentration of S2O32- , t is the time in seconds between mixing and the appearance of the blue color. In order to obtain reasonable reaction times, it is necessary to use initial rate intervals which allow the Fe3+ concentration to decrease slightly (about 4 to 10 percent) from its initial value. To compensate for this change, it is suggested that the average Fe3+ concentration during this time interval be used in place of the initial concentration.
PROCEDURE
Cautions 1. Be careful about performing all the experiments at the same temperature since temperature changes affect the rate constant; use water bath to keep temperature constant. 2. HNO3 does not participate in the reaction between ferric and iodide ions but it is used to prevent hydrolysis of the Fe3+ in the water environment. 3. Use 50 mL burettes to dispense H2O, Fe(NO3)3, and HNO3 solutions; 10 mL pipettes to dispense the KI and Na2S2O3 solutions, and a 10 mL graduated cylinder to dispense the starch solution.
exp
0.04M Fe3+ 1 2 3 4 5 6 7 8 0.15M HNO3 H2O
10 15 20 25 30 10 10 10
10 50 10 10 10 10 10 10
30 30 30 30 30 30 30 30
10 10 10 10 10 5 15 20
10 10 10 10 10 10 10 10
5 5 5 5 5 5 5 5
25 25 25 25 25 30 20 15
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2.
Swirl the contents of each beaker for a short time and place the beakers in a constant temperature water bath set at room temperature to reach temperature equilibrium (10 to 15 minutes will be sufficient for this).
3.
Meanwhile, prepare the solutions for experiment 2 in a second set of beakers, and place these beakers also in the water bath. By this time the solutions for experiment 1 should be at water bath temperature.
4.
Measure and record the initial temperature of the solutions, then simultaneously start the timer and add (rapidly) the contents of the 100 mL beaker to the 250 mL beaker. You may remove the solutions temporarily from the water bath to do this.
5. 6.
Swirl the solutions until mixed, then return the 250 mL beaker to the water bath. Stop the timer at the first appearance of the blue color. Again measure the temperature, and calculate the average temperature of the solution during the reaction. Record the time interval, t in Table 1 in your report sheet.
7. 8. 9.
Clean and dry the beakers, add the solutions for experiment 3, and place the beakers in the water bath. Then measure the temperature of the solutions for experiment 2, mix the solutions and follow the same procedure as for experiment 1. Continue in this manner through experiment 5.
B. Reaction order with respect to I1. This part is performed exactly as in Part A, except that the concentration of ferric ion is kept constant while the concentration of iodide ion is varied. The composition of the various reaction mixtures to be used is given in Part A.1 Table for Experiments 6, 7 and 8.
CALCULATIONS
1. Fill up the Table 3 in your report sheet. a) Calculate [S2O32-]i which is constant in all experiments. b) Calculate initial reaction rate by using time data above. c) Take logarithm of the rate. d) Calculate initial Fe3+ concentration. e) Calculate average Fe3+ concentration by using the equation below:
[Fe 3 + ] =
av
( [Fe
3+
] i + [Fe 3 + ] f / 2 4 10 4 / 2 = [Fe 3 + ] i 2 10 4
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2. 3. 4. 5. 6.
Calculate initial I- concentration. This will be equal to average I- concentration. Take logarithm of average I- concentrations. Plot log rate vs. log[Fe3+]av for experiments 1 to 5. Find the slope of the line, this will be equal to a, reaction order with respect to ferric ion. Plot log rate vs. log[I-]av for experiments 1, 6, 7, 8. Find the slope of the line, this will be equal to b, reaction order with respect to iodide ion.
QUESTIONS
1. 2. 3. 4. What is the overall rate order of this reaction? Calculate the reaction rate constant, k, of this reaction. Comment on any deviation which could be observed in Experiment 5. Comment on the long period needed to observe blue color in Experiment 6.
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15
Le Chatelier Kural
Kimyasallar
0.1 M nikel nitrat 6 M amonyum hidroksit 6 M hidroklorik asit CaCl2 zeltisi Na2CO3 zeltisi 6 M HCl
AMA
Le Chatelier Kuraln kimyasal reaksiyonlar zerinde uygulamak.
TEORK BLG
1884 Ylnda Henri Le Chatelier tarafndan ileri srlen kurala gre dengedeki bir sisteme dardan herhangi bir etki yaplrsa (deriim, scaklk ve basn gibi artlarn deitirilmesi), sistem bu etkiyi azaltacak yne kendiliinden kayar. Bu deneyde yeil renkli sulu nikel nitrat zeltisi, amonyak zeltisinin ilave edilmesiyle mavi renge dnerken hidroklorik asit zeltisi ilavesiyle de tekrar yeil renge geri dner. Bazen amonyak ilavesiyle kelti oluumu gzlenir. kelti, asit ilavesiyle znr.
NOT: Nikel nitrat zeltisi toksiktir. Konsantre asit ve baz zeltileri sradnda derinizi yakar ve kyafetlerinize zarar verir. NH3 buharna kar dikkatli olun ve NH3 zeltisi hazrlarken eker oca kullann. Deney srasnda eldiven ve koruyucu gzlk kullanlmal.
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Uzun formdaki 1 L'lik behere, 350 mL nikel nitrat zeltisi ve bir tane manyetik balk koyarak beheri manyetik kartrc zerine yerletirin. Oda scaklnda kartrlan karma renk maviye dnnceye kadar amonyum hidroksit ilave edin. Maviye dnen karma bu sefer de hidroklorik asit zeltisinden renk yeile dnnceye kadar ilave edin. Eer isterseniz son iki ilemi yeni nikel nitrat zeltisi kullanmadan bir kez daha tekrar edebilirsiniz (yani srasyla amonyum hidroksit ve hidroklorik asit ilavesiyle renk deiimlerini gzlemleyebilirsiniz). Nikel-su kompleksi yeil, nikel-amonyak kompleksi ise mavi renklidir. Amonyak ilavesiyle dengedeki sistem saa kayar ve renk maviye dner. Amonyan ortamdan uzaklatrlmasyla da (HCl ilavesi) dengede ki sistem tekrardan sola kayarak balang rengi yeile dner. [Ni(H2O)6]+2(aq) + 6NH3 [Ni(NH3)6]+2(aq) Bazen, kelti oluumu gzlenebilir. Nikel zeltisine, asit ilave edildiinde oluan kelti znr. Ni(NO3)2(aq) + 2NH4OH(aq) Ni(OH)2(k) + 2NH4NO3(aq)
CO3-2 iyonlar, asitle Le Chatelier Kuralna gre reaksiyona girer. 1. Reaksiyon sola kayarak CaCO3 znr, 2. ve 3. reaksiyonlarda da grld gibi CO2 gaz k gzlenir. Deneyde kullanlacak kimyasallar: CaCl2 zeltisi, Na2CO3 zeltisi, 6 M HCl. 25 mL CaCl2 zeltisini 400 mL'lik behere koyun. zerine, 25 mL Na2CO3 zeltisi ilave edin. kelti oluumunu gzlemleyin. 5mL 6 M HCl'i reaksiyon karmnn bulunduu behere ilave edin. Kat keltinin yok oluunu ve gaz kn gzlemleyin.
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16
AMA
Standart bir asit zeltisi yardmyla bazn deriiminin belirlenmesi.
TEORK BLG
Deriimi bilinen bir zelti ile reaksiyona giren deriimi bilinmeyen zeltinin hacminin belirlenmesi ilemine titrasyon denir. Bir zeltideki asit miktar, bu zeltinin, deriimi bilinen standart bir baz zeltisi ile titrasyonu sonucu bulunabilir. Bir titrasyonda asit veya bazlardan birinin tamamen reaksiyona girdii noktaya edeerlik noktas denir. Titrasyon devam ederken, edeerlik noktasnn duyarllkla belirlenmesi gerekir. Deriimi bilinmeyen asit veya baz zeltileri, deriimleri kesin olarak bilinen baz veya asit zeltileri ile titre edilerek deriimleri bulunur. Her titrasyon ileminde deriimi belirlenmi standart zelti gereklidir. Standart zelti, ok saf maddelerden balon joje kullanlarak hazrlanr. Titrasyonun tamamlanmas, edeerlik noktasna ulap ulamad indikatr yardmyla anlalr. Titrasyon, gerekte bir ntrallemedir. ndikatrn rengi H3O+ iyonunun OH- iyonu tarafndan balanmas ile deiir. Asit-baz titrasyonlarnda kullanlan indikatrler farkl pH aralklarnda renk deitirirler. Kullanlacak indikatrlerin seiminde buna dikkat edilmesi gerekir. Asit-baz titrasyonlarnda kullanlan indikatrler ntralleme annda renk deitiren zayf asit veya bazlardr. rnein, fenolftalein indikatr zayf bir organik asittir, bunu HIn ile simgelersek, HIn suda az oranda H+ ve In- 'a ayrr. HIn + H2O
renksiz
In- + H3O+
pembe
Kuvvetli bir asit, rnein HCl, NaOH ile titre edilirken ok az miktarda indikatr HCl zeltisine damlatlr. Bu zelti renksizdir. Titrasyon srasnda NaOH nce HCl ile reaksiyona girer ve onu ntralletirir. Ntralleme gerekleince, yani edeerlik noktasna ulanca eklenen son NaOH
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damlas HIn ile reaksiyona girer ve NaIn tuzunu oluturur. Bu tuz, Na+ ve koyu pembe Iniyonlarndan olumutur. Bylece titrasyonun dnm noktas pembe rengin grlmesiyle belirlenmi olur. Kartrlan iki zeltinin hacimleri llmse ve bunlardan birinin deriimi biliniyorsa dierinin deriimi hesaplanabilir. Bu deneyde, nce NaOH zeltisi, deriimi bilinen bir asit ile ntralletirilecek ve bazn deriimi belirlenecektir. Daha sonra da baz zeltisi, deriimi bilinmeyen bir asidin deriimini belirlemekte kullanlacaktr.
DENEYN YAPILII
Fenoftalein ieren baz ilalarn insanlarda kansere sebep olduu tespit edilmitir. Bu bileikle alrken, eldiven ve koruyucu gzlk kullanlmaldr.
0.005 M standart slfrik asit zeltisi hazrlayn. Laboratuvardaki deriimi bilinmeyen NaOH zeltisinden temiz bir behere 25 mL aln ve buna 175 mL su ekleyerek seyreltik bir NaOH zeltisi yapn. Tamamen karncaya kadar alkalayn. 50 mL'lik temiz bir breti nce damtk su ile ardndan da iki kere 5'er mL kendi yaptnz NaOH zeltisiyle alkalayn. Breti doldurun ve balang dzeyini okuyun. erlene 15'er mL baz zeltisi aln ve 2 damla fenolftalein zeltisi ekleyin. Bretteki baz zeltisini boaltn, nce damtk su sonra da iki defa 5'er mL standart asit zeltisi ile alkalayn. Bret iinde hava kabarc kalmayacak ekilde standart asit zeltisi ile doldurun. zelti dzeyini 0.1 mL duyarllkta okuyun. NaOH zeltilerinin herbirini standart asit zeltisiyle titre edin. lk erlendeki zelti yaklak dnm noktasn belirlemek iin kullanlacaktr. lk erleni hzl hzl kartrarak srekli bir pembe renk grnceye kadar abuk bir ekilde asit zeltisi ekleyin. Bu ilemi gerekletirirken breti sol elinizle idare ederken erleni sa elinizle alkalamalsnz. Erlenin altna beyaz bir kat koyarsanz pembe rengi daha kolay grrsnz. Bretteki zelti dzeyini okuyun, bu sonu size dier zeltileri daha dikkatli titre etmenizi salayacaktr. Gerekli olduunu tahmin ettiiniz asit zeltisinin yzde yetmi beini bretten erlene aktn. Bu arada asit zeltisini srekli olarak kartrn. Erlenin i yzeyini pipetten pskrteceiniz damtk suyla ykayn. Pembe renk en az 30 s kalncaya kadar kartrarak, damla damla asit zeltisini ekleyin. Bretteki asit zeltisinin dzeyini okuyun.
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Asistannzdan deriimi bilinmeyen bir slfrik asit rnei aln. Breti ykayn ve deneye yukarda anlatld ekilde devam edip bilinmeyen asidin deriimini bulun.
SORULAR
1. 2. ndikatr nedir? Dnm noktasn belirlemek iin fenolftalein yerine hangi indikatrler kullanlabilir. Gravimetrik analiz ve volumetrik analiz nedir? Aklaynz.
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17
pH ve ndikatrler
AMA
pH kavramn renerek, indikatrleri tanmak. Bir zeltinin pH'n belirlemek amacyla, indikatrlerin nasl kullanlacan renmek.
TEORK BLG
pH, hidronyum iyonlar deriiminin negatif logaritmas olarak tanmlanr (pH = -log[H3O+]). Kimyasal problemlerde olduu kadar biyolojik ve ntral ortamlarda da nemi byktr. Asit-baz indikatrleri, zayf asit ve zayf baz olan organik molekllerdir ve proton aldklarndan protonlanmam biimlerinde farkl renkler verirler. Zayf asit olan bir indikator iin (In-)'in (HIn)'e oran H+ 'nn deriimine baldr.
H+ + In-
HIn
[H + ] [In - ] [HIn]
zeltide In- ok olduunda baz rengi, HIn ok olduunda indikatrn asit rengi gzlenir. Genel olarak aadaki artlar salandnda asit-baz rengi gzlenebilir. Her indikatrn, pH birimlerine ve Ki deerine dayanan zel bir renk deitirme aral vardr. rnein, fenolftalein renk deitirme aral pH=0-10 arasndadr. Asit rengi renksiz; baz rengi ise pembedir. 5x10-3 M NaOH zeltisine 1 damla fenolftalein zeltisi ilave edildiinde zelti rengi pembe olacaktr. [OH-]=5x10-3 M, [H+]=2x10-12 M, pH= 11.70 ise (pH=10 baz rengi) zelti pembe renk olur. pH pKi asit rengi gzlenir. pH pKi baz rengi gzlenir. PH = pKi renk deitirme aral.
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DENEYN YAPILII
Fenoftalein ieren baz ilalarn insanlarda kansere sebep olduu tespit edilmitir. Bu bileikle alrken, eldiven ve koruyucu gzlk kullanlmaldr.
Hazrlam olduunuz 10-3 M HCl zeltisinden 5 mL alp 45 mL kaynatlm damtk su ekleyerek seyreltin. zeltiyi iyice kartrn. Son zeltinin H+ iyonu deriimi 10-4 M (pH=4)'dr. pH=4 olan bu zeltiden 5 mL aln ve buna 45 mL kaynatlm damtk su ekleyerek pH=5 olan bir zelti hazrlayn. pH' be olan bu zeltiden 5 mL aln ve buna 45mL kaynatlm damtk su ilave ederek pH=6 olan bir zelti hazrlayn. Ayn ekilde hazrladnz 10-3 M NaOH zeltisini de seyrelterek pH' 10, 9, 8 olan zeltiler hazrlayn. Hazrladnz her bir zeltiden 5 mL alarak temiz ve kuru olan deney tplerine koyunuz. Her deney tpne 2 damla metil oranj indikatr zeltisinden damlatnz. Deney tplerini iyice alkaladktan sonra oluan renkleri aadaki tabloya not ediniz. ki tp alp bunlardan birine 5 mL 0.10 M H3BO3 zeltisi dierine ise 5 mL 0.050 M NH3 zeltisi koyup bunlara da 2 damla metil oranj indikatr zeltisinden damlatnz. Oluan renklerin hangi pH'taki standart zeltinizle uyutuunu yaznz. Yukardaki ilemleri, metil krmzs, bromtimol mavisi, fenolftalein ve alizarin sars indikatrleri iin tekrarlaynz.
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2.
ndikatr Metil oranj Metil krmzs Bromtimol mavisi Fenolftalein Alizarin sars
Renk (amonyakla)
3. 4.
H3BO3 ve NH3 'n iyonlama reaksiyonunu yazp ayrma sabitlerini hesaplaynz. Deneyde kullandnz zayf asit ve zayf bazn ayrma yzdesini hesaplaynz.
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18
OBJECTIVE
To study a number of chemical reactions that involve the transfer of electrons from a reducing agent to an oxidizing agent. To establish a qualitative chemical redox couple table for seven redox couples by mixing the oxidized form of one redox couple with the reduced form of another couple and observing whether a reaction takes place. The redox couples are Cu(II)/Cu, Zn(II)/Zn, Fe(II)/Fe, H+/H2, Fe(III)/Fe(II), Br2/Br-, and I2/I- .
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75
Note that no electrons appear in the overall reaction. This is why it may sometimes be difficult for you to look at a chemical reaction and try to decide whether it can be classified as an oxidation-reduction reaction. Keep in mind the fact that this decision is arbitrary. Certain conventional rules have been adopted about the definition of oxidation number. We will classify a reaction as an oxidation-reduction reaction only if there is a change in oxidation state (or oxidation number) of atoms involved in the reaction according to our previously defined rules. (These rules are summarized in Study Assignment A, together with some examples of how they are applied.)
Cu
2+
FIGURE 18-1 Direct chemical reaction of zinc with Cu2+. As the zinc dissolves, Cu is plated out on the surface of the zinc. A Cu2+ ion is reduced by transfer of two electrons from a Zn atom.
Cu
Cu
Zn
zinc metal
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a greater affinity for electrons than copper(II) ion. Another way of looking at this competition is to say that copper metal is a stronger reducing agent than is silver metal, because copper atoms give up their electrons more easily than do silver atoms. Strictly speaking, we need to look at the tendency to transfer electrons from one species to another as a property of each redox couple, because the tendency of a Ag(I) ion to accept an electron and become a silver atom depends on the difference in the Gibbs energy between an Ag(I) ion and a silver atom and the tendency of the copper atom to give up two electrons and become a Cu(II) ion depends on the difference in the Gibbs energy of the copper atom and the Cu(II) ion. So we are really comparing the tendency of redox couples to exchange electrons in an oxidation-reduction reaction. Thus it is only possible to arrange the various oxidizing and reducing agents as redox couples in a table, according to their relative tendencies to gain or lose electrons. In this experiment, we shall explore such relative tendencies for a limited number of reactions.
FIGURE 18-2 Schematic diagram illustrating the most powerful and the weakest oxidizing and reducing agents.
Li+ + e-
Li
Fluorine is one of the strongest oxidizing agents known, and lithium is one of the strongest reducing agents; therefore these two redox couples would be at opposite ends of the table, with most other redox couples falling somewhere in between. (See Figure 18-2.)
PROCEDURE
NOTE: Before beginning this experiment, complete the preliminary exercise in your experiment report form, indicating as directed there the substances oxidized and reduced in the several equations given and the change in oxidation state, if any.
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SAFETY PRECAUTIONS: Hexane is volatile and flammable. Carry out the tests requiring hexane in a fume hood away from all open flames. WASTE COLLECTION: The metal wire or strips should be collected, and can be reused if they are cleaned off. A waste container should be provided, in the hood if possible, for the hexaneand methanol-containing mixtures. Also collect the metal ion solutions in a beaker, neutralize with NaHCO3(s), and put the solid residue in a waste container.
A. A Qualitative Redox Series for Copper, Zinc, Iron, and Their Ions
Explore the behavior of small pieces of Cu, Zn, and Fe metals (if the iron is rusty, it should first be cleaned in 6 M H2SO4, then rinsed in water), putting each metal in 3 mL of 0.1 M solutions of the ions of the other metalsthat is, Cu with Zn2+ and with Fe2+, Zn with Cu2+ and with Fe2+, and Fe with Cu2+ and with Zn2+to determine the order in which the redox couples should be placed in a table like that shown in Figures 18-2 and 18-3. The metal ion/metal couple that appears lowest in the table will correspond to the metal that visibly reacts with all the other metal ions and is therefore the strongest reducing agent. Sometime the evidence for reaction is subtle. Keep in mind that when most metal ions are reduced chemically they do not produce a shiny metal surface. More often the metal deposited is in the form of finely divided crystals that appear black or brown. Write equations for the reactions that occur. Solutions containing Fe2+ should be freshly prepared by dissolving 0.1 g of FeSO4 7H2O in 3 mL of water. Note that the oxidized form of one redox couple is always mixed with the reduced form of the other couple, or vice versa. (The oxidized form of the couple is always the one with the higher charge or higher oxidation number.) Prepare a table as directed in the report form, under part 1 of the Experimental Data.
+eOA
stronger
RA
stronger
OA OA OA OA - e-
RA RA RA RA
FIGURE 18-3 Tendencies for reactions between oxidizing and reducing agents. The dashed arrows indicate possible redox reactions. An oxidizing agent can react with any reducing agent that lies below it in the table.
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C.
First, if you are not familiar with the colors of the free halogens in hexane, add a little Br2 water to 3 mL of H2O and 1 mL of hexane. (Caution: Hexane is flammable.) Mix the liquids together by shaking, and observe the color of the hexane layer floating on top. Dispose of the hexanesolution mixture in the appropriate waste container. Repeat, using 0.05 M I2 in methanol instead of Br2 water. Dispose of these mixtures in the appropriate waste container. Now explore the behavior of 3-mL samples of 0.1 M solutions of KBr and KI (with 1 mL of hexane added to each) when each is treated with a little of the other free halogenthat is, mix KBr with a few drops of I2 in methanol, and KI with a few drops of Br2 waterto determine the relative order of the Br2/Br- and I2/I- redox couples. Dispose of these mixtures in the appropriate container. Write equations for the reactions that take place. Then arrange the two halogens in a separate redox couple table, as directed in the report form.
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F. Summary of Data
Your experimental observations, together with the preceding data, will enable you to combine your two separate redox couple tables into one general redox couple table. The final table will contain all seven redox couples studied and show the relative tendencies of the various elements and ions to lose or gain electrons. Note that each redox couple is written so that the change from left to right represents gain of electrons (reduction). In the table in your report form, designate clearly which are the reducing agents, which are the oxidizing agents, which end of each column is the stronger (S), and which end is the weaker (W). Such a table can be expanded to include many more oxidation-reduction couples and is useful in predicting the course of many reactions. (Refer to Table 10 in the Appendix.) In reading Table
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10, note that any oxidizing agent (in the left column) has the possibility of reacting with any
reducing agent (in the right column) that lies below it in the table (see Figure 18-3). The table
makes no prediction, however, of the rate of a given reactionsome reactions are too slow to be practical. Also, you should note that the concentration of the ions in a solution has a definite effect on the tendency for reaction, in accordance with the Le Chatelier principle. BIBLIOGRAPHY Sisler, H. H., and VanderWerf, C. A., "Oxidation-Reduction: An Example of Chemical Sophistry,"
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19
OBJECTIVE
To understand the relation between the molar solubility and the solubility product constant of a sparingly soluble salt. To measure the molar solubility of calcium iodate in pure water and to determine the solubility product constant. To investigate the common ion effect by measuring the molar solubility of calcium iodate in a solution containing added potassium iodate.
THEORY
When soluble ionic compounds are dissolved in water, the solution usually contains just the ions that were present in the solid salt. For example, in a saturated solution of KNO3, the solution contains only K+ ions and NO3- ions, and the dissolved salt is completely dissociated.1
KNO3(s) K+(aq) + NO3-(aq)
(1)
In solid KNO3 each ion is surrounded by ions of the opposite charge. This is still largely true when the KNO3 is dissolved in water, but the ions are farther apart and each ion is surrounded by a cluster of water molecules that are more or less tightly bound to the ion. The ions in solution are therefore said to be "hydrated" or "aquated."
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When a salt is sparingly soluble it suggests that the attractive forces between the ions in the solid are greater than the attractive forces between the ions and the solvent (usually water). Many sparingly soluble salts do not completely dissociate into the ions present in the solid, but interact with one another to form aggregates, called complexes, or react with water to form new species. For example, a saturated solution of Ca(OH)2 contains Ca(OH)+ ion as well as Ca2+ and OH- ions, as shown by the following equilibria:
Ca(OH)2 (s) Ca(OH)+ (aq) Ca(OH)+ (aq) + OH-(aq) Ca2+ (aq) + OH-(aq)
(2) (3)
A saturated solution of CaCO3 contains appreciable concentrations of HCO3- and OH- as well as Ca2+ and CO32- ions. Here, carbonate ion (CO32-) reacts with water to produce bicarbonate ion and hydroxide ion as shown in the following equilibria:
CaCO3(s) CO32- (aq) + H2O Ca2+(aq) + CO32- (aq) HCO3- (aq) + OH-(aq)
(4) (5)
The behavior shown in Equation (5) is typical of all salts (such as carbonates, sulfides, and phosphates) in which the anion can react with H2O to form an acid that is only weakly dissociated. The two examples whose solubility equilibria are described by Equations (2) through (5) show that it is not always safe to make the assumption that only the ions produced by complete dissociation of the salt are present. The solubility behavior of every salt must be determined by an experimental investigation.
The Relation Between Molar Solubility and the Solubility Product Constant
Calcium iodate, the salt you will study in this experiment, has been shown to be completely dissociated in water into calcium ions, Ca2+, and iodate ions, IO3-.2
Ca(IO3)2 (s) Ca2+ (aq) + 2 IO3- (aq)
(6)
For any salt that dissolves to give just the ions originally present in the salt there is a simple relation between the molar solubility of the salt and the solubility product constant of the salt. The concentration of each ion will be equal to the molar solubility or equal to some multiple of the molar solubility.
The actual composition of the solid that is in equilibrium with the ions in solution is the hexahydrate, Ca(IO3)2 6H2O.
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What do we mean by the molar solubility of the salt? This quantity is just the concentration of the dissolved salt, expressed in units of moles per liter. In the calcium iodate example, the calcium ion concentration is equal to the molar solubility, and the iodate ion concentration is equal to two times the molar solubility. This will be true because each mole of calcium iodate that dissolves gives one mole of calcium ions and two moles of iodate ions. If we let the symbols s represents the molar solubility of calcium iodate (in units of moles per liter), the concentrations of Ca2+ and IO3- ions will be related to the molar solubility, s, by the following equations:
[Ca2+] = s [IO3-] = 2s
(7) (8)
Equation (6) shows the reaction for the dissociation of solid Ca(IO3)2 in a saturated aqueous solution. The equilibrium constant expression for this reaction (often called the solubility product expression) is written as shown in Equation (9), observing the convention that the activity of the pure solid is taken to be equal to 1 so that it does not appear in the equilibrium constant expression.3
Ksp = [Ca2+] [IO3-]2
(9)
If we substitute for the concentration of each ion its equivalent in units of molar solubility, s, by substituting Equations (7) and (8) into Equation (9), we obtain an equation that shows that there is a simple relation between the Ksp and the molar solubility of the salt.
Ksp = [Ca2+] [IO3-]2 = s(2s)2 = 4s3
(10)
The situation is more complicated in the case of calcium hydroxide, Ca(OH)2. The equations for the dissociation of Ca(OH)2 are written as shown in Equations (2) and (3) with equilibrium constant expressions given by
K2 = [Ca(OH)+][OH-] K3 =
[Ca 2 + ][OH - ] [Ca(OH) + ]
(11) (12)
The relationship between the molar solubility, s, and the concentrations of the ions in solution is obtained by summing the concentrations of the species that contain Ca2+ (calcium material balance):
[Ca(OH)+] + [Ca2+] = s
3
(13)
The effective concentration, or "activity," of a pure solid that participates in a chemical reaction does not change. By thermodynamic convention the pure solid is chosen as the thermodynamic reference state, which is equivalent to assigning the value 1.00 to the activity of solid.
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or by summing the concentrations of the species that contain OH- (hydroxide material balance):4
[Ca(OH)+] + [OH-] = 2s
(13)
Substitution of Equations (11) and (12) into Equations (13) and (14), respectively, with elimination of [Ca2+] and [Ca(OH)+] leads to the equation
K2 K3 = [OH-]2 ([OH-] s)
(15)
This result shows that it is necessary to know both s and [OH-] in order to have enough information to calculate K2 and K3. To summarize we emphasize two important points about solubility equilibria: (a) The identity of all of the solution species in equilibrium with the solid must be determined by experiment. It is not safe to assume that all salts dissociate completely to give just the ions in the solid salt, (b) The solubility product constant can be calculated directly from the molar solubility only if the dissolved salt completely dissociates into its constituent ions, these ions neither reacting with one another to form complexes nor reacting with water to form weak acids or bases. In the case of calcium iodate, a single equilibrium describes the system, and the value of the equilibrium constant can be calculated from the molar solubility. For the other salts we described (Ca(OH)2, CaCO3), it requires two equilibria to describe each system, and a measurement of just the molar solubility does not provide enough information to calculate two equilibrium constants.
(16) (17)
Equation (14) contains the implicit assumption that the dissociation of water produces a negligible contribution to the OH- concentration.
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Note that all of the calcium ion must come from dissolved calcium iodate. However, the iodate ion comes from both KIO3 and dissolved Ca(IO3)2. As before, we get two moles of iodate ions and one mole of calcium ions for every mole of calcium iodate that goes into solution. The relation between the solubility product constant and the molar solubility will also be changed (compare Equation (18) with Equation (10)).
Ksp = [Ca2+][IO3-]2 = s (0.01 + 2s)2
(18)
If we know the concentration of potassium iodate, a single measurement of the total iodate concentration allows us to calculate the molar solubility of calcium iodate and the solubility product constant.
(19)
(20)
Note from the overall stoichiometry that each mole of IO3- will produce enough I2 to consume 6 moles of S2O32-. Therefore the concentration of IO3- ion will be given by
-
[IO 3 ] ,
mol mL S 2 O 3 = L mL IO 3
mol S 2 O 3 L
1mol IO 3
(21)
6mol S 2 O 3
PROCEDURE
NOTES TO INSTRUCTOR: The instructions are given for reduced scale measurements using a 1mL microburet. The iodate containing sample volumes may be measured using 1- and 2-ml serological pipets or weighing the samples (1.00 g = 1.00 mL). If you prefer to use larger samples and a 50-mL buret, increase the volume of iodate containing samples to 10 mL in parts 1, 2, and 3 and use 0.05 M Na2S2O3 as the titrant. The 10-mL sample containing iodate is added to a 250-mL Erlenmeyer flask containing 50 mL deionized water, 2 g
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KI, 10 mL 1 M HCl, with the addition of 5 mL of 0.1% starch indicator when the solution has turned from brown to yellow. Sodium thiosulfate pentahydrate that has been kept in a well-sealed bottle is normally pure enough so that a solution made up by accurately weighing the salt will be within 1% of the target concentration, so that standardization of the solution is not absolutely necessary. As an option the standardization of the nominal 0.15 M Na2S2O3 may be performed by the students if they are supplied with a solution of 0.0100 M KIO3. The titration is performed as described for the determination of the molar solubility of calcium iodate. The solid in equilibrium with the saturated solution of calcium iodate is the hexahydrate. We have found, however, that use of anhydrous calcium iodate to prepare the saturated solutions gives the same results. Anhydrous calcium iodate is available commercially, but a quantity of the hexahydrate sufficient for 100 students is easily prepared. Dissolve 0.5 mol (112 g) of KIO3 in 600 mL of hot water in a liter beaker. To the hot solution, slowly add with stirring 0.25 mol of Ca(NO3)2 (or CaCl2) dissolved in 200 mL water. Allow to cool. Filter off the solid on a large Bchner funnel and wash the solid with three 50-mL portions of cold water. Allow the solid to air dry or use the moist cake to prepare the saturated solutions. The saturated solution in pure water is prepared by adding 8 g Ca(IO3)2 6H2O per liter of water. The saturated solution in 0.0100 M KIO3 is prepared by adding 2.14 g KIO3 + 4 g Ca(IO3) 6H2O per liter of water. Stir the solutions for at least 24 h, then allow to stand for 48 h before use. Ideally, the solutions should be thermostatted at 25C, but if this is not possible a temperature correction can be made to estimate the molar solubility at 25C using data at a different temperature (see Problem 2 of the Report form). Use a siphon or centrifuge individual 5-mL samples so that students may receive samples that are free of particles of solid calcium iodate.
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mL of deionized water in a 10- or 25-mL Erlenmeyer flask. Add 0.2 g KI and swirl to dissolve. Record the temperature of the saturated calcium iodate solution. Obtain a 5-mL sample of saturated calcium iodate solution in a 13 x 100 mm test tube. (If the sample shows any visible solid particles it should be centrifuged to settle them to the bottom of the tube.) Then pipet 1.00 mL of the saturated solution to the Erlenmeyer flask. (A 1.00-mL serological pipet may be used or, if one is not available, weigh out 1.00 0.02 g (1 g = 1 mL) of sample directly into the Erlenmeyer flask, using a fine-tipped polyethylene pipet to dispense the sample solution.) Then add 1 mL of 1 M HCl. The solution should turn brown. Without delay, titrate the solution with sodium thiosulfate until the solution is yellow. Then add 1 mL of 0.1% starch indicator; the solution should turn blueblack, the color of the starch-iodine complex. Continue the titration until you get a sharp change from blue to a colorless solution. Record the final buret reading. Repeat the titration procedure with a second sample. The volumes should agree to within 5 to 10%. (A possible source of error is the air oxidation of I- to give I2. This will result in values that are too high if the solution is allowed to stand for too long before it is titrated.) Calculate the concentration of iodate ion in the sample of saturated solution (see Equation (21)). The molar solubility of calcium iodate will be equal to one half the iodate concentration (see Equations (7) and (8)). Calculate the solubility product constant for calcium iodate (see Equation (10)).
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20
Sabun
AMA
Sabunun yapln renmek ve sabun rneindeki su yzdesini bulmak.
TEORK BLG
Yalarn alkali hidroksitleri ile hidrolizi sonucu oluan karboksilik asitlerin sodyum veya potasyum tuzlarna sabun ve bu hidrolize sabunlama denir. Ya asitlerinin sodyum tuzu beyaz sabun, potasyum tuzu ise yumuak sabun (arap sabunu) dur. Yalar, teorik miktardan biraz fazla alkali hidroksit zeltisi ile uzun sre kaynatlarak veya su ile basn altnda yksek scaklkta stlarak hidroliz edilir. Sabun yapmnda ya asitlerinin sodyum tuzlar, sodyum klorr ile ktrldkten sonra geriye kalan sulu zeltide gliserin bulunur. Suyun buharlatrlmasyla gliserin elde edilir. zeltiden ayrlan sabun birka kere su ile ykanarak tuzlardan temizlenir ve basn uygulanarak kalplanr. Beyaz sabunda %60-70 sabun, %0.2-0.5 tuz ve %30 su vardr.
O H2C HC H 2C O C O O O C O C (CH2)16 (CH2)16 CH 3 + 3NaOH CH 3 HC OH + 3 Na +O(CH2 )16 CH 3 H2C OH O C (CH 2)16 CH3
H 2C
OH
Gliserin
Triailesteri (triailgliserol), bitkisel ve hayvansal yalardr. Oda scaklnda sv halde bulunan triailgliserollere sv yalar; kat halde bulunanlara kat yalar ad verilir. ail grubu da ayn
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olan triailgliseroller basit triailgliserollerdir. Ail gruplarnn farkl olduu triailgliseroller ise kark triailgliserollerdir ve en yaygn olandr. Bu deneyin ilk ksmnda hayvansal veya bitkisel bir ya (byk molekll esterler karm) ile NaOH zeltisinin reaksiyonundan sabun elde edilecektir. Deneyin ikinci ksmnda, sodyum stearat ierdii kabul edilen bir sabun rneindeki su yzdesi belirlenecektir. Miktar bilinen bir sabun rnei, deriimi bilinen bir asidin belirli hacmiyle kartrlacak ve stearat iyonunun hidronyum iyonu ile reaksiyona girmesiyle stearik asit ktrlecektir. Daha sonra da hidronyum iyonunun ars deriimi bilinen bir baz ile titre edilecektir. Bir mol stearat iyonu ile bir mol hidronyum iyonu reaksiyona girdii iin sabun ile reaksiyona giren hidronyum iyonunun mol says orijinal rnekteki sodyum stearatn mol saysna eit olacaktr. Sodyum stearatn molekl arlndan ve rnein orijinal ktlesinden rnekteki su yzdesi hesaplanacaktr.
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SORULAR
1. 2. Birinci ksmda sabun elde edilirken ortama neden NaCl ilave edildi? Aklaynz. Zeytin ya, susam ya, fndk ya ve soya yanda hangi ya asitleri bulunur? Aratrnz. Ya asitleri arasndaki farkllklar aklaynz.
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References
1.
Laboratory Experiments for Chemistry, John H. Nelson, Kenneth C. Kemp, Prentice-Hall Inc, New Jersey, 7th edition, 1997.
2.
Chemistry in the Laboratory, Julian L. Roberts Jr, J. Leland Hollenberg, James M. Postma, W.H. Freeman and Company, New York, 1st edition, 1997.
3.
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