Laredo Community College

Science Department CHEM 1411 Laboratory 77

Solutions: Spectroscopy and Concentration

Formation of [Cu(NH !4"# Comple$ %on A. Introduction
Review Sections 4.5 4.6 (Concentration of Solutions and Solution Stoichiometry) in your textboo (Chemistry: The Central Science, 10th Ed. ! "rown! #e$ay! "ursten! % "urd&e). Read the to'ic (& Clo'er Loo() *'ing Spectro'copic Met+od' to Mea'ure ,eaction ,ate' ) for an introduction about the s'ectro'hotometer. Read cha'ter *4 for a discussion of the chemistry of coordination com'ounds. +his ex'eriment studies the formation of a coordination com'ound containin& a com'lex ion! ,Cu(-./)40*1. +he com'lex ion is formed between a transition metal cation! Cu *1! and four neutral ammonia molecules. +he - atom of the ammonia molecules contains an unshared electron 'air! which it donates to the Cu*1 ion and forms a coordinate covalent bond. "ecause the Cu *1 ion has an un'aired electron (2s* *s* *'6 /s* /'6 /d3 4s4) in the /d subshell! the ion has a 'ale a5ua blue color6 com'lexation of the ammonia molecules results in the color chan&in& to a very dee' blue ( nown as royal blue). "ecause the ion is hi&hly colored! it absorbs li&ht in the visible re&ion of the electroma&netic s'ectrum. +he intensity of li&ht absorbed is directly 'ro'ortional to the concentration of the ion. +he ex'erimental 'rocedures you have 'erformed this semester have 'rovided visible results6 however! the 'rocedures have commonly been time consumin& and cumbersome! and the results de'ended u'on your s ill as an analyst. +hese 'rocedures also re5uired you to wor with 5uantities ran&in& from 4.*5 /.4 &rams of substance. Commonly! an analytical chemist or chemical technician is only 'rovided sam'les of less than 4.2 &ram total! and thus re5uire that a different techni5ue be utili7ed to determine the identity of an un nown sam'le. 8ne such techni5ue involves instrumental analysis usin& a s'ectro'hotometer. +his techni5ue is es'ecially valuable if the solution is colored. S'ectrosco'ic techni5ues rely on the ability of solutes in solution to absorb electroma&netic radiation (li&ht) as it 'asses throu&h the sam'le. 9t low concentrations of a solute in solution! the absorbance of the li&ht is directly 'ro'ortional to the concentration! and can be determined from "eer:s #aw! where & is the amount of li&ht absorbed! is the molar absor'tivity constant for the solution at the s'ecific wavelen&th! b is the 'ath len&th throu&h which the li&ht must 'ass (i.e.! the diameter of the cuvette) and C is the solute concentration. &-bC (.eer/' La0!

;urin& the ex'eriment you will record data for the amount of li&ht transmitted ('asses) throu&h the solution. +he absorbance is related to the < transmittance by the ex'ression & - 1log (2341552!6 +he transmittance is the ratio of the intensity of li&ht 'assin& throu&h a solution ( %) and the intensity of li&ht 'assin& throu&h 'ure solvent (%5). 3 - (%4%5!

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=n this ex'eriment you will be determine the concentration of an un nown solution by measurin& the amount of li&ht transmitted throu&h the solution. +he concentration will be determined by the &ra'hical analysis techni5ue em'loyed in the 'revious ex'eriment ( Solution') Concentration and Den'ity). ,eaction') +he addition of ammonia to the co''er(==) sulfate is a two>ste' 'rocess. =n the first ste'! solid co''er(==) hydroxide is formed. +he Cu(8.)* (s) dissolves as additional 5uantities of ammonia are added in the second ste'. (1! ("! Cu"# (a8! # " NH
(a8!

# " H"9 (l! Cu(9H!" ('! # " NH4# (a8!

(a8!

Cu(9H!" ('! # " NH4# (a8! # " NH

[Cu(NH !4:"# (a8! # " H"9 (l!

+he overall net e5uation for the reaction is ( ! Cu"# (a8! # 4 NH

(a8!

[Cu(NH !4:"# (a8! 6

B.

Procedure
Preparation of the Complex Ion Tetraamminecopper(II) Sulfate S'ectro'hotometer! bea ers (/4>! 54>! 244>! and *54>m#)! 24>m# $ohr 'i'ets! 'i'et 'um's! 54>m# &raduated cylinder! 24 test tubes (2/ x 244 mm)! test tube rac s! stirrin& rods! wash bottle! @imwi'es a'rons! &o&&les! fume hoods ;istilled water! 4.454 M CuS84! 6 M -./ solutions! An nown CuS84 Solutions

E$erci'e 16

Apparatus? Safety Equipment? Chemicals? O !ecti"es: 2. *.

=n this ex'eriment you will learn how to? 're'are solutions by dilution and to determine the molarity of the diluted solutions. use a visible s'ectro'hotometer to measure 'ercent transmittance (<+) of a colored solution.

%n'truction') #ef$re c$min% t$ la , the instruct$r &ill ha"e placed a spectr$ph$t$meter $n each side $f the ench. '$u &ill &$r( in a %r$up $f three $r f$ur. Each student &ill pr$"ide t&$ $r three ea(ers f$r the e)periment.

CHEM 1411 Lab

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,efer to t+e laminated card for t+e in'truction' to operate t+e 'pectrop+otometer6 *art 1. *reparati$n $f S$luti$ns ,efer to 3able 1 belo0 for 8uantitie' of CuS94 and 0ater needed to prepare t+e 'olution'6

Table . "ea er 1 " 4 ; < = > *n(no0n

Buantities -eeded to Cre'are the Solutions Folume CuS84 (m#) 165 "65 "65 "6; 465 <65 >65 1565 1565 Folume .*8 +otal Folume (m#) "465 " 65 1465 =6; <65 465 "65 565 565 ";65 ";65 1<65 1565 1565 1565 1565 1565 1565

2. +urn on the s'ectro'hotometer with the 8-D8EE switch (left dial on front of the instrument) and set the wavelen&th to 454 nm (dial on to' of s'ectro'hotometer). "e sure that the lam' is on. =f the lam' is off! turn in on with the switch on the bac left bottom corner of the s'ectro'hotometer. +he instrument needs to warm u' at least *4 minutes 'rior to use.

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*.

8btain two 24>m# $ohr 'i'ets and 'i'et 'um's and a bottle of < M NH from the cart at the front of the lab. =n addition! obtain 54 m# of 565;5 M CuS94 in a &raduated cylinder and transfer it to a clean 244>m# bea er (the 565;5 M CuS94 serves as a stoc solution for 're'arin& the dilute solutions). Clace a''roximately 254 m# of distilled water in a *54>m# bea er.

/. #abel ten bea ers from (4) > (G) and (A). "ea er (4) will be used to 're'are a (blan ) to adHust the 244< transmittance for the s'ectro'hotometer. "ea er (2) must be a 244>m# bea er. 4. Cre'are the blan by addin& *4 dro's (eyedro''er) of + M -./ (C&*3%9N) &mmonia fume' can irritate t+e eye'? u'e under t+e fume +ood) to 24 m# of distilled water in bea er (4). +his blan will be used to 7ero the s'ectro'hotometer. 5. 8btain the un nown sam'le from your instructor! and write the un nown number on the data sheet. 6. Cre'are the remainin& nine solutions accordin& to +able 2! usin& one $ohr 'i'et for the CuS84 solution and the second $ohr 'i'et for the water. Ase an eyedro''er to add *4 dro's of + M -./ (C&*3%9N) Fume') to each bea er. Ase a clean stirrin& rod to com'letely dissolve the solid co''er(==) hydroxide which forms as an intermediate. (9 54>m# &raduated cylinder may be used for the water for bea ers (2) and (*).) +he com'lex ion that forms will be dee' blue in color for the more concentrated solutions.

I. Calculate the molarity of solutions 2>G usin& the dilution e5uation C1@1- C"@" . (-ote? 9mmonia is added in excess 5uantity to each solution. "ecause the volume of ammonia is constant! we will i&nore the volume of -./ in our calculations.)

*art ,. -easurement $f . Transmittance G. Clean and dry ten 2/ x 244 mm test tubes. Aou 0ill get t+e be't re'ult' if you u'e te't tube' from t+e 'ame manufacturer6 Remove any 'a'er labels from the sides of the tubes. -umber the test tubes 4 G and (A). -ote the location of the manufacturer:s mar (white oval or hexa&on) on each test tube. 3. +ransfer 5.4 m# of the (blan ) into test tube (4)! and 5.4 m# of each solution into test tubes 2 G. +ransfer 5.4 m# of the un nown solution into test tube (A). 24. Refer to the s'ectro'hotometer instruction card and set the instrument to dis'lay < transmittance and absorbance data (8bHective *). +hen o'en the lid to the sam'le holder and remove any test tube inside the chamber. Close the door and adHust the <+ to 4 with the 8-D8EE switch.

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22.

Ase a @imwi'e to clean the outside of the test tube containin& the blan solution. Clace the test tube containin& the blan inside the sam'le holder! with the manufacturer:s mar ali&ned with the notch on the sam'le holder and close the door. 9dHust the <+ to 244< usin& the ri&ht nob on the front of the instrument. Remove the blan and adHust the 7ero transmittance! followed by re'lacin& the blan and adHustin& the 244< transmittance if necessary. ("e sure the test tube is 'ro'erly ali&ned with the notch on the sam'le chamber.) Ji'e the outside of test tube K2 with a @imwi'e! and insert into the sam'le chamber. Chec the ali&nment of the test tube. Close the sam'le holder door! and allow the dis'lay to settle down. Record the < + on the data sheet. Re'eat the two 'revious ste's with each of the remainin& test tubes containin& the nown solutions and the un nown solution. #et the instructor examine your results to see if any measurements need to be re'eated.

2*.

2/.

24. Jhen you have finished! discard the solutions in the bea ers and test tubes in the sin with 'lenty of runnin& water. Clean the &lassware! and return any borrowed items to the cart at the front of the room. D9 N93 3*,N 9FF 3HE SBEC3,9BH939ME3E,6 93HE, S3*DEN3S M&A NEED 39 *SE 3HE %NS3,*MEN36

!.

"esults
*art 1. Estimati$n $f /n(n$&n C$ncentrati$n O !ecti"es: /. 4. =n this 'ortion of the ex'eriment you will? convert <+ values to absorbance values. estimate the concentration of an un nown solution from &ra'hical data..

During t+e lab period you 0ill obtain an e'timated Calue for t+e molarity of t+e un(no0n 'olution by grap+ing your data6 3o complete t+e laboratory reportD you 0ill create a grap+ in a Micro'oft E$cel 'pread'+eet and u'ing t+e 'pread'+eet formula' to determine t+e be't 'traig+t1line fit for t+e data and interpolate t+e curCe to find t+e concentration of t+e un(no0n6 2. *. Ase the ex'ression & - 1log(234155! to convert each 'ercent transmittance value from ste's 24>22 to absorbance. (#) 8n the reverse side of the data sheet are two &rids for ma in& &ra'hs of your data. 8n the to' &rid! 'lot the data for 23 C'6 molarity6 ;raw the best smooth curve which fits the data. (=t will not be a strai&ht line.)

CHEM 1411 Lab

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/.

8n the bottom &rid! 'lot the data for ab'orbance C'6 molarity6 Ase the six>inch ruler from your des to draw the best strai&ht>line fit for your data. Note) 3+e be't curCe fit doe' not nece''arily mean Econnect1t+e1dot'E6 Some of t+e data point' may be aboCe t+e curCeD 0+ile ot+er' 0ill be belo0 t+e curCe6

4.

Eind the absorbance of the un nown solution on the y>axis. ;raw a hori7ontal dotted line across the &ra'h until it intersects with the data curve. Jhen the two lines meet! draw a vertical dotted line to the x>axis. +he molarity of the dotted line re'resents the concentration of the un nown. ($)

*art ,. 0raphical Analysis $f 1ata /sin% A Spreadsheet O !ecti"es: 5. 6. =n this 'ortion of the ex'eriment you will learn how to? create &ra'hs in a s'readsheet! and obtain best>line fits for the data in'ut formulas into a s'readsheet to analy7e the data and to determine a more accurate value for the concentration of the un nown solution.

5. 8'en the s'readsheet (Spectro'copy) from the C.L$ 2422 website. Eill in your name! section! and date (mm4dd4yy) in the s'ecified cells. 6. Lnter the molarity of the CuS84 stoc solution in cell D<. ;o not include the unit M in the cell. I. Lnter the volume of CuS84 solution used in cells .15).1=! and the volume of water used in C15)C1=. Lnter the < transmittance values for each solution in cells F15)F1=. G. Lnter your un nown K in cell F<! and the <+ in cell F1G. Aou are no0 ready to enter t+e formula' 0+ic+ 0ill +elp you create t+e grap+' and analyHe t+e data6 3. $ove the cursor to cell D15! and ty'e the followin& formula in the cell. ;o not include the 5uotation mar s. Cress the RL+AR- ey after ty'in& the formula. (-IdI< J b154(b15 # c15!) 24. $ove the cursor bac to D15! and clic on the KC9BAL icon (two sheets side by side) in the toolbar at the to' of the s'readsheet. +he cell outline will chan&e from solid lines to dashed lines.

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22. .i&hli&ht cells D11)D1= by holdin& the left mouse button while you slide throu&h the cells. Clic on the KB&S3EL icon to co'y the formula from D15 into these cells. $ove the cursor throu&h the hi&hli&hted cells. Mou should observe that the contents of the formula chan&es to include only the volumes used in each sam'le. .owever! the first 'art of the formula! IDI<! remains constant in each formula. ;ollar si&ns are used in formulas when the contents of a cell are constant in a series of calculations. 2*. $ove the cursor to cell F15 and ty'e the formula (-(11 J log(f154155!!). Cress return to enter the formula. Re'eat the copy 7 pa'te 'rocedure for cells F11)F1=. 2/. Mou now have all the data necessary to draw the &ra'hs usin& $icrosoft Lxcel. Clic the KC+art MiHardL icon on the toolbar. Select KNA (Scatter!L as chart ty'e. Select (-extN) to &o to ste' *. 24. +y'e (Od15)d1=Df15)f1=) in the data ran&e box. Select (-extN) to &o to ste' /. 25. Clic on the (+itles) o'tion. Lnter K[Cu(NH !4:"#L as (Chart title)! KMolarityD ML as (Falue (P) axis)! and K2 3L as (Falue (M) axis). Clic on the (#e&end) o'tion! and turn off the (Show le&end). Select (-extN) to &o to ste' 4. 26. Select (Einish) to 'lace the &ra'h on the wor sheet. .i&hli&ht the &ra'h to 'osition it in cells O )N1< (or somewhere nearby to the ri&ht of the data). 2I. Clace the cursor on the &ra'h and clic to modify the a''earance as follows. a) ;ouble clic inside the chart to (Eormat Chart 9rea). Choose the followin& o'tions. Catterns9rea Eont Jhite 24 't 9rial

b) ;ouble clic the x>axis to (Eormat 9xis). Choose the followin& o'tions. Catterns $aHor tic mar s Cross $inor +ic $ar s =nside +ic mar labels -ext to axis Scale $inimum $aximum $aHor tic mar s $inor tic mar s 24 't 9rial 4 decimal 'laces 4 4.454 4.424 4.44*5

Eont -umber

CHEM 1411 Lab

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c) ;ouble clic the y>axis to (Eormat 9xis). Choose the same o'tions as for the x>axis exce't the scale. Scale $inimum 4 $aximum 244 $aHor tic mar s *4 $inor tic mar s 5 d) Sin&le clic one of the data 'oints to hi&hli&ht the series. Ander the main s'readsheet headin& (Chart) select K&dd trendlineL. Choose KE$ponentialL ty'e. Clic (8@). +hen hi&hli&ht the trendline! and chan&e the wei&ht (thic ness) of the trendline to sin&le width. Aou +aCe no0 fini'+ed t+e grap+ of concentration C'6 percent tran'mittance6 3+e ne$t 'tep i' to create t+e grap+ of concentration C'6 ab'orbance6 3+e 'tep' are almo't identicalD 0it+ minor modification'6 2G. Clic on the KC+art MiHardL icon to create a second PM (Scatter) &ra'h. Select (-extN) to &o to ste' *. +y'e (Od15)d1=Dg15)g1=) in the data ran&e box. Select (-extN) to &o to ste' /. 23. Clic on the (+itles) o'tion. Lnter K[Cu(NH !4:"#L as (Chart title)! KMolarityD ML as (Falue (P) axis)! and K&b'orbanceD &L as (Falue (M) axis). Clic on the (#e&end) o'tion! and turn off the (Show le&end). Select (-extN) to &o to ste' 4. *4. Select (Einish) to 'lace the &ra'h on the wor sheet. .i&hli&ht the &ra'h to 'osition it under the first &ra'h (O"1)N 4!. *2. Mou will use the same &ra'h o'tions as you did for the first &ra'h! exce't for the y>axis scale. Scale $inimum 4 $aximum 244 $aHor tic mar s *4 $inor tic mar s 5 **. Select K&dd trendlineL from the s'readsheet headin& (Chart). Choose KLinearL ty'e. Clic (8@). +hen hi&hli&ht the trendline! and chan&e the wei&ht (thic ness) of the trendline to sin&le width. */. Lnter the followin& formulas in the indicated cells. An nown Concentration Slo'e y>interce't Cell D1G D"1 D"" Formula -trend(d15)d1=Dg15)g1=Dg1G! -inde$(line't(g15)g1=Dd15)d1=!D1! -inde$(line't(g15)g1=Dd15)d1=!D"!

CHEM 1411 Lab

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R* correlation

D"

-r'8(g15)g1=Dd15)d1=!

*4. Save the results on your lab flo''y dis . +hen 'rint the s'readsheet containin& the data and the two &ra'hs. 9 sam'le data set and &ra'hs are attached after the data sheets.

!.

%aboratory "eport

Mou should include the followin& items in your lab re'ort. =. ==. ===. =F. Mour name! +itle! % ;ate of Lx'eriment -ames of your laboratory 'artners Lx'erimental 8bHective(s) one or two sentences 'er exercise Crocedure as QRefer to lab handout RQ Results ;ata Calculated values Concentration of un nown solution F. ;iscussion and Conclusions 1iscuss y$ur results, !ustifyin% y$ur ch$ice $f un(n$&n c$ncentrati$n fr$m the e)perimental data and results. 2nclude a discussi$n $f p$ssi le s$urces $f err$r, especially &ith re%ards t$ the 3 , data c$rrelati$n c$efficient. F=. 9ttachments

CHEM 1411 Lab

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Laredo Community College

Science Department CHEM 1411 Laboratory 87

Solutions: Spectroscopy and Concentration

Formation of [Cu(NH !4:"# Comple$ %on !ATA S&''T (ame: Cartner(s)
"alanced L5uation? Concentration (C1) of CuS84 stoc solution 4.454 M -./ 6 M

Section

!ate

Solution (2) (*) (/) (4) (5) (6) (I) (G)

Folume (@1) of CuS84 2.4 m# *.4 m# *.4 m# *.5 m# 4.4 m# 6.4 m# G.4 m# 24.4 m#

Folume of .*8 *4.4 m# */.4 m# 24.4 m# I.5 m# 6.4 m# 4.4 m# *.4 m# 4.4 m#

+otal Folume (@") *5.4 m# *5.4 m# 26.4 m# 24.4 m# 24.4 m# 24.4 m# 24.4 m# 24.4 m#

,Cu*10! C" 5655"5 M M M M M M M M

<+

An nown K Concentration of An nown Solution

<+ M (from &ra'h of & vs. C)

S+o0 all calculation' on a 'eparate '+eet of paper6 Eor Solution K 2? C1 - 565;5 M @1 - 165 mL

C1 @1 - C" @" @" - ";65 mL

C" - (C1 @1!4 @" - (565;5 M!(165 mL!4(";65 mL! - 5655"5 M

CHEM 1411 Lab

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[Cu(NH3)4]2+ 100 90 80 70 60 50 40 30 20 10 0 0.0000

%T

0.0100

0.0200

0.0300

0.0400

0.0500

Molarity, M

[Cu(NH3)4]2+
1.0 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.0 0.0000

Absorbance, A

0.0100

0.0200

0.0300

0.0400

0.0500

Molarity, M

CHEM 1411 Lab

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(ame Concentration? S'ectrosco'y

C.L$ 2422 ;ate

Section

$olarity of CuS84 Solution! M Sam'le 1 " 4 ; < = > *n(no0n 'lope y1intercept ," correlation mL CuS94 2.4 *.4 *.4 *.5 4.4 6.4 G.4 24.4 mL H"9 *4.4 */.4 24.4 I.5 6.4 4.4 *.4 4.4

4.454 C" 4.44*4 4.4444 4.446/ 4.42*5 4.4*44 4.4/44 4.4444 4.4544

*n(no0n P 23 33.* 34.5 3/.G II.3 4/.I **.5 26.6 2*.5 5I.4 & 4.44/5 4.4*46 4.4*IG 4.24G5 4./535 4.64IG 4.II33 4.34/2 4.*442

5651;
*4.6 >4.46II6 4.3II

CHEM 1411 Lab

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[Cu(NH3)4]2+
100 80

%T

60 40 20 0 0.0000

0.0100

0.0200

0.0300

0.0400

0.0500

Molarity, M

[Cu(NH3)4]2+
1.2

Absorbance, A

1.0 0.8 0.6 0.4 0.2 0.0 -0.2 0.0000 0.0100 0.0200 0.0300 0.0400 0.0500

Molarity, M