synthesis of cobalt complex lab report

synthesis of cobalt complex lab report

MWof[Co(diNOsar)]Br3=674gm/mol Springborg,R.J.GeueandM.R. Inthisexperiment[Co(diNOsar)]Br3issynthesisedfrom[Co(en)3]Br3inthe Possible structures of the cobalt (III) bis-(Iminodiacetato) complex, University of the Witwatersrand, Johannesburg, Introduction to Criminology: Victims and Reduction of Crime (cmy1502), Academic information management (AIM 111), Legal aspects of electronic commerce (LML4810), Law of Payment and Negotiable Instruments (NEG321), Law of Succession and Administration of Estates (LPS321E), Mathematics for Natural Sciences (MATH150), Alternative Dispute Resolution 431 (ADR431), Collective Bargaining and Collective Labour Law 503 (JMLV503), Chapter 12 - Complete - Summary Law of Contract 202[4], Integrated Marketing Communication Ch 1-4, 377716306 Evidencia 1 Evaluacion Herramientas Para La Definicion de Proyectos, PVL1501 Notes and longer questions and answers, MRL3701 CASE Summary - CASES SUMMARIES FOR INSOLVENCY LAW, Accounting 1B assignment 1 Answer Booklet 1, ISC3701 Assignment 03 MARK 100/100 Year 2021, (6) Just Administrative Action - Setting the Scene, IND2601 Study notes - Summary African Customary Law, Online Exp06 - Thin Lenses - Lab Report 2447573-1, Casework Process Report Fifth Session MARK045100, PVL1501 Notes 2 LAW of PERSONS help you study. Hambley,J.MacB. Finally1 Astheabsorbancebandsfortwo Metalionsthatareboundinsidecagecomplexare /F4.0 13 0 R /F6.0 14 0 R /F7.0 15 0 R /F3.0 16 0 R >> >> 1) Report the yields and colors of the salenH 2 ligand and the various salen complexes. Week 3. 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They also scattered the light which was characteristic of crystals. Syntheses are based on procedures from: Angelici, R. J. Synthesis and Technique in Inorganic Chemistry. A handout called "The Cobalt Complex Project-Synthesis" was given by the instructor. Rc:OJI/O%^e)=\OC] Mo2O$ 3. complexcomparedtothe[Co(diNOsar)]3+ When it was reacted with NH 3 a dark blue The main objective of this experiment is to carry out qualitative analysis to identify metal cations in unknown solution 1. C`SA\U1*OCaa"xhi|Pi.4XO {g4'd"wggG>Cv#([qR6i"|-Fs (FC#21GfeJ0"l9ncRY?4RnAzEoA[#Q8Gqf(hI|hE>4ai#,G>> G>8g(Agf)AL F y[XW)LQe\i`d]9[SNbLG)n"o8DLe~|I4-l-MJ]aiXfiXB85O7K"~96y0;LLe ;anajfb f@K4U`L( c%lh9f`h V@/8f/ &l7xkiu1@k,07NPnO,e n/g,koQya|"S3gy7Y@Ig yww . Factsheet 3 - ts purpose is to protect the child's rights to develop his or her full cognitive. electronicpropertiesofthesetwocomplexesalongwith[Co(sep)]Br3were 5, synthesis of [Co(diNOsar)]3+ octet) can produce complexes with them more easily [5]. J. Chem. It did not form any precipitate with ammonium chloride but formed a very light white precipitate, which is identical to barium nitrates reaction against sulfuric acid. alsoshowsbothoxidationand During the experiment it reacted very similarly to Iron (III) nitrate and Barium nitrate. Preparation of Chloropentammine Cobalt(III) Chloride In this lab, we, PDF) Cobalt Complexes: Introduction and Spectra Analysis, Solved Experiment 1 Isomerism in the Cobalt(III) Complex | Chegg.com, https://www.gnu.org/licenses/gpl-2.0.html, good title for research paper about abortion. Whereas triethylenetetramine coordinates to form a, , symmetry axis, tris (2-aminoethy) amine forms a complex that has a, The purpose of the lab is to synthesize a cobalt (III) that is prepared by using cobalt (II), the, amine, and reagent which convert cobalt(II) to cobalt(III). These isomeric configurations are that of the trans-fac, the trans-mer and, the cis isomers. successfullyinvestigatedusingUVVisspectroscopyandcyclicvoltammetry.. Question: This is the balanced equation for this reaction; 2 KOH + 2NH(CH Co H2 2 ) 2 + CoCl 2 .6H 2 O = K 2 [Co(NH(CH CO2 2) ) ]2 2 +8H 2 O + 2HCl, The brown complex that was yielded was most likely the trans-fac geometric isomer of the, Cobalt (III) bis-(Iminodiacetato) complex. The synthesis of the coordination complex trans- dichloro bis (ethylenediamine)cobalt(III) chloride is a classic experiment and can provide an opportunity for inclusion of diverse concepts if additional activities are incorporated. This was because Cis isomer, (or violet compound) had a higher affinity for the resin due to its dipole, all the more, electronegative groups were on the same side of the central atom. To browse Academia.edu and the wider internet faster and more securely, please take a few seconds toupgrade your browser. ISXIf&K;^:K3H(>M[ 2h:!]b.A34n01U"&.ar.J]Tn5-T$#4{L_}?gnR6#[trzOMRgIuo!ORdNp2\"{$$7m'3MIIP!'9TC%Pt(4s'07i|2\9"VN4BN=%TC1jOkfi The percent yield of the compound was not 100% due to small errors throughout experiments such as losing some of the compound during transferring, more liquid evaporating than desired, and not measuring volume to exact accuracy and precision every time. In contrast to the trans-mer geometric isomer, the, trans-fac isomer was more stable due to the more favourable bond angles on the nitrogen, when the Iminodiacetic acid (IDA) is in the facial configuration, hence, the more stable, compound was formed. doubletsbeingquitesmall. They also scattered the light which was characteristic of crystals. 3167 NH 3 (N-H Any unused cobalt complex will be saved for later use. The violet complex that was obtained was most likely the cis-fac geometric isomer since this was the only possible isomer that could be formed by performing the reaction at cool temperatures [1] . CageLigandsarethreedimensionalmultidentateligandsthatarecapableof voltammetry(CV). insidethecageeventhoughitisnotconsideredtobethermodynamically obtained. : an American History (Eric Foner), Business Law: Text and Cases (Kenneth W. Clarkson; Roger LeRoy Miller; Frank B. Cobalt salts react with solutions containing chloride ion, and ammonia to produce different complexes containing cobalt, ammonia, and chlorine. The minimum amount of NH 3 was used to neutralize acetyl acetone. x\s_G. 0oN @ Ea]?0;IS)$nJ;>Z-Nvo]y?-R_?~P,8O] o_g t:Gd8~$2_/-)7|CN&x!Ox2*#<3kN(L|VgS>Mq3~FJw[?, qhq,)\7E0%IE_`jw)Qcbyo~yW+Tv_RYeCe[aF0Ov!O+q\,PQ#\VknU%q_yOws%I6>ORYvBhB5: es.P)/[\Z|hCR^^/Mqn+Mq*/_*/P#57k@x3'BsyxG|z,J\`& ck/W~' Fyar_FZR6e{y=' z/WjPyU\N5 &gCpye?~WQK2*SNj(Nf>gT@{ ^*zP*ki&:[& GX*=1 V\E?r4F\! 1 shows the XRD patterns of copper carbonate powder. ataround580mV(figure.3). A yield of protonsattachedtothesamecarbonatomsontheethylenediaminestraps crystals were obtained and not anything else. Journal of . structureofthecomplex. The crystals were then observed under a microscope. The minimum amount of NH3 was used to neutralize acetyl acetone. Exp 1B cm- Functional group Literature Value (cm- [Co(sepulchrate)]3+ The stability of this complex was measured by investigating its reactivity with a few reagents. withintheCVtimescaleanddoesnotreadilyexchangeligandsaswasthe obtained but since there was some spillage, most of the product was lost [3], seefigures 4 into a blue-violet colored Co complex and measuring the absorbance in the Spec 20 instrument. This laboratory experiment outlines the use of modern instrumentation such as UV-Vis spectrophotometer for thermal ligand substitution monitoring, and the magnetic susceptibility balance for confirmation of the electron configuration of the cobalt(III) center in trans-dichlorobis(ethylenediamine)cobalt(III) chloride. TheABquartetisconsistsofthetwosetsofpeakscentredat4and TheUVVisspectraof g of KOH which was also dissolved in the same solution. For example, when the graduated cylinder was filled with 100 mL deionized water and the liquid was poured into a flask, the liquid measured over the 100 mL mark on the flask, meaning that. At a reaction ratio of 1.08, paratacamite (Cu_2 Cl(OH)_3 ), beside alkali copper carbonate, was formed because of incomplete reaction at a copper content of 53.9 wt%. Aims ionisnotstable. [ (1:<6Ds]5m(sK..o8mApMsX;VnI0c&|I0`Nvk7KvZQsQ=FwUScP=0+0|IlNuBtfq"&=(>;0/z u&gX#aAy6L|i(7Hrd%)N`}xGD -u:|CfYJ!. ]Q >X}]IK84hu What is the purpose of using H2O2 in the synthesis? electrochemicalpropertiesofthecomplexesandUVVisspectrophotometryto 5 Snow,J. The color of the solution didnt change after dissolving ammonium chloride in concentrated aqueous ammonium hydrioxie. hbbd```b``6A$L"e3&w{H {&g{vOvOi??vO^~x77\>nysCn#x:f1w_w8ojM~Rc@8/D')%1CwEw$8Ce\!}eQ4+~|(E?|/__n_7Z~3 mJf)r{7t>e_e[_l^]{snp8X({t1u>|9^ywTrm2Y1[ak-8bn~t@Q-Tt |dZA>|oi-Fd>}d>ga;R6OG>_bm# [O#f1DZSkL#|WoU;myN.HWH{)C|a{(kbu`89>52 ^;\9;;`V1{r,}P"eX&*ZFQcD+21Z3T.FymZSj%gYK+l1!F)q^_ +*#`g34~qd]bCKik;h_t/[W? out with suction and dried in vacuo. In Inorganic Syntheses; Wiley-Blackwell, 2007; 222225. constituteandAABBspinsystem. 2M'"()Y'ld42'&Sg^}8&w,\V:k;iR;;\u?V\\C9u(JI]BSs_ QP5FzG%t{3qWD0vz \}\ $um+C;X9:Y^gB,\ACioci]g(L;z9AnI TheCVspectrumof[Co(en)3]Br3hasshownthatareductionpeak The reactivity of the bis (acetylacetonato) copper complex was low due to its exceptional stability. manipulatedtoproducecagecompoundsthatexhibitselectivebinding After the product had crystallized, it was filtered out with 5ml of dH2O followed by 10 ml ethanol. (review sheet 4), 1-3 Assignment- Triple Bottom Line Industry Comparison, Scavanger Hunt - Human anatomy scavenger hunt, Leadership class , week 3 executive summary, I am doing my essay on the Ted Talk titaled How One Photo Captured a Humanitie Crisis https, School-Plan - School Plan of San Juan Integrated School, SEC-502-RS-Dispositions Self-Assessment Survey T3 (1), Techniques DE Separation ET Analyse EN Biochimi 1. Under a hood, seven grams of cobalt (II) carbonate (CoCO3) were added to fifteen mL of 12M HCl in a 250 mL beaker. Abstract Thispatternarisesfromthecouplingbetweentheprotonsnearestto stream The trans-fac isomer was more positive than the cis isomer, thus it was eluted first [4] . 1521 0 obj <> endobj ( g"l]gFd! "D'`*A+"`FL3D2#g^c|F>.RBPL8'= KqZ K# |5MY-iY7KMDzq8V\3FpI8L5I{@v|0]Jk~tR1GdI)gAPO*>T2LvXcr%r~d=zT*#tZu..IWf\-9?>RbcXQFV,L/IK>JvT_ zy*L&>c*b3Mc45^ Harrodield,JM,Lawrance,GA,&1985,Sargeson,AM, willbeinvestigatedusingcyclicvoltammetrytoexaminethe A millilitre of 30% H 2 O 2 was then added at a very slow rate. The neutralized solution The 2 0 obj Co(II)ionisformedtheligandsarereadilyexchangedduetothe x}IrE$Rnf~7@,4GxcwsqGC]_knnhfgy>>! When viewed under a microscopic both compounds were similar to tiny pieces of broken, glass. 1 Conclusion cage. Oncethereactivehigh The crystal We will synthesize the unknown compound with concentrated ammonia, Cobalt (II) Chloride Hexahydrate, 30% H2O2, and concentrated HCl. arealsofoundtovarybetweenthetwocomplexeswiththecage Copper(II) chloride solution was the lightest shade of blue and Cobalt chloride solution was the darkest. exchangeligandsall6CoNbondswouldneedtobreakatthesametimein and[Co(en)]3+ The crystal were filtered Little abundant on the Earth's surface, cobalt is obtained from the extraction of ores and the most common oxidation states for this element are +2 and +3. geometryaroundthemetalionremainedunchangedbetweenthecomplexes. Journal of Chemical Education . Copyright 2018 The Author(s). PDF) Synthesis of cobalt(III) coordination complex and modifying it to chloropentamminecobalt(III) chloride. complex. thetwocomplexes. 1 0 obj This brings the ligands in close to allow them to react and hence form the propertiestowardscertainmetalions. Moreover, unknown 3 reacted similar to Barium nitrate when it was tested against ammonium chloride and sulfuric acid. Analysis of the Cobalt Complexes Collect a uv-vis absorbance spectrum for each complex. The solution was cooled in an ice bath and the product crystallised. geometry on the ligands due to the formation of a complex with the metal. The bis-(acetylacetonato) copper (iii) complex, Limiting reagent: The1 This is done in the introductory section of the manual, the individual lab introductions, and through extension questions requiring research about traditional, more hazardous experimental methods. reversible oxidation of the Co(II) ion to Co(III) ion. to occur. Thissplittingpatternisalsoduetothe The crystal environment of the cobalt ion is different in the two isomers, so they have different colors. A infrared spectra of the product was then obtained. The color of the solution didn't change after dissolving ammonium chloride in concentrated aqueous ammonium hydrioxie. stream %%EOF 6(5):159-163, Jocelyn Pineda Lanorio1, Jerry Gomez Lanorio2, 1Department of Chemistry, Illinois College, Jacksonville, IL, USA, 2Division of Mathematics, Science and Physical Education, Lincoln College, Lincoln, IL, USA. The precipitate was filtered with A. Synthesis of [Co (NH3)5Cl]Cl2 We weighed approximately 4.0 g of powdered cobalt chloride 6-hydrate in a 125mL Erlenmeyer flask. muchinterestin producemoreproduct. The experiment was carried out according to the detail directions written on the paper. Added 5 grams of cobalt carbonate to 20 mL of hrdrobromic acid in a beaker. The reason for irreversible Cyclicvoltammetrypart: Describe any unusual observations and possible reasons for low yield. These isomeric configurations are that of the trans-fac, the trans-mer and the cis isomers. Current(uA) absorbancebandsininorganiccomplexesisdependantonthegeometryand Creaser,J.MacB. ThispeakcorrespondstothereductionofCo(III) beduetogreaterdistortionoftheoctahedralgeometryinthecage When the obtained product was mixed with chloroform there was no reaction. 2 0 obj The Infrared spectra of the brown and violet compounds both had, a band at 1623 cm -1 revealing that complexes of cobalt (III) with Iminodiacetic acid were. Bailar, J. C.; Rollinson, C. L. Cis- and Trans- Dichlorobis(Ethylenediamine)Cobalt(III) Chloride and the Resolution of the Cis Form. After the product had crystallized, it was filtered out wi th 5ml $Bn~PixTiFXZ^eiNfm Anr$* HCl also reacted with the product to yield a dark green dissolved solution. 2014, 113 (2), 321331. through the duration of the entire experiment. AstheCo(III)ionsare A.; Fenske, D.; Fedin, V. P. Syntheses, Structures, and Electrochemical Properties of Inclusion Compounds of Cucurbit [8] Uril with Cobalt(III) and Nickel(II) Complexes. 1542 0 obj <>/Encrypt 1522 0 R/Filter/FlateDecode/ID[<1C24A38AA750414F9E7C0176128FEB28><1763AFA170AF484C8E19E02D3DA823CB>]/Index[1521 55]/Info 1520 0 R/Length 101/Prev 322935/Root 1523 0 R/Size 1576/Type/XRef/W[1 3 1]>>stream Two possible coordination complexes will be synthesized in this experiment. Soc.,106,5478(1984). The mixture was cooled down to 12oC in an ice bath. The solutions color started changing after putting cobalt(II) chloride hexahydrate. The manual helps students understand the timing and situations for the various techniques. It can be concluded that the compounds that were formed were actually pure since the experimental values of IR are closely related to those obtained from literature. Under the hood, add 2.5 g of ammonium chloride to 15 mL concentrated aqueous ammonia in a 125-mL Erlenmeyer flask. M,I8? However, when the carboxylic acids are coordinated to cobalt (III) this signal shifts to a value that is approximately 1630cm-1 . While in the hood, we dissolved 2.0 g of ammonium chloride in 12 mL of concentrated ammonia in a separate beaker and added the mixture to the flask of CoCl 2 and swirled to dissolve. ,}Tr.6;XAo,p[fY '9rW7f{,mTo "B86"WkYFD@ .% N/ad endobj [ua+d=? speciesthe series of chlorine substituted cobalt acetylacetonate complexes[Co(acac)x(acac-Cl)3-x], x . Reasonsforthelowyieldincludethedifficultyingettingallofthe ZEQHxl;' "G>dFyF#pF )5?rxG!DKF:n6bMb0afSf| 0w$7Qe6t6 consideringthenatureoftheethylenediamineligands. The aim of this experiment was to prepare and systematically investigate the coordinating structures and properties the bis-type complex of Cobalt with Iminodiacetic (IDA) acid and copper with acetyl acetanato anion. Experiment #9: Synthesis and Percent Cobalt Analysis of a Coordination Compound and Kinetics of Aquation of a Cobalt (III) Coordination Compound. CoNbondsconstantlybreaking. and toCo(II). 2008, 85 (4), 532. There are three possible bis- type geometric isomers of Cobalt that can be synthesized. productcrystallizingoutofsolution. additional 45 minutes. 2 Thistypeofsynthesis % The iron is first presented in its Fe2+ form, so it must first be oxidized to, In this experiment, a sample of K2S2O8 was prepared by the electrolysis of an aqueous solution of H2SO4 and K2SO4. [ 6h90he~NjCPVJ'le~L+kw%`o"+& os>WM>]z(iR!t_zt' K@# Id>S):Nz'G\9,zj2y2daPbTvX1 +o..CJ0>#5@QPp!p5N=@H)UkGAm$}?c]@+ /TD. Thestructureofthepreparedcomplex,[Co(sepulchrate)]3+ All the reactants were coordinated into complexes, which also indicates for a high yield. This new feature enables different reading modes for our document viewer.By default we've enabled the "Distraction-Free" mode, but you can change it back to "Regular", using this dropdown. The precipitate was filtered with suction and was washed repeatedly with water acetone and a small amount od ether. Szafran, Z. Microscale Inorganic Chemistry: A Comprehensive Laboratory Experience, J. Wiley: New York, 1991, 239-242. The experiment was carried out according to the detail directions written on the paper. from the IR spectra of all the bis-(acetylacetonato) copper (iii) complex 1952, 50 (1), 69126. The Cobalt (III) bis-(Iminodiacetato) complex. Figure 1: Possible structures of the cobalt (III) bis-(Iminodiacetato) complex, Bis(acetylacetonato) copper(II) is a complex that results from the coordination of copper with 4 0 obj A millilitre of 30% H2O2 was then added at a very slow rate. You will need to write balanced chemical equations for the two different redox reactions that you will use in this analysis. TheCVspectrumof[Co(en)3]Br3doesnotshowaoxidationpeak The reaction mole ratio of sodium carbonate to copper chloride (II) was controlled from 1.08 to 1.68. 6 No. mixture was covered with a watch glass and was kept at the water bath at 80 oC for an The book is used for many students who learn in chemical, whether in chemical analys, pure chemical, etc. The objective of this work was to. Its formula is written [Co (NH 3)4Co3]NO3. Lack of sodium carbonate may cause incomplete reaction with copper chloride (II) because of low pH (6.0) of the solution [12]. 3 0 obj Table 2: Table showing the peaks and their possible functional groups that where obtained from the IR spectra of all the bis-(acetylacetonato) copper (iii) complex, Similar to the cobalt complex, a strong band at 1730 cm-1 means that there are free carboxylic acids in the compound. For example, with it was tested against Ammonium Chloride, the color of the solution changed to a light green, very identically to Iron (III) nitrate and Ammonium Chloride. http://creativecommons.org/licenses/by/4.0/. Two grams of Iminodiacetic acid was dissolved in the same solution followed another mass of 1.6 g of KOH which was also dissolved in the same solution. Copyright 2023 StudeerSnel B.V., Keizersgracht 424, 1016 GC Amsterdam, KVK: 56829787, BTW: NL852321363B01, Biological Science (Freeman Scott; Quillin Kim; Allison Lizabeth), Educational Research: Competencies for Analysis and Applications (Gay L. R.; Mills Geoffrey E.; Airasian Peter W.), The Methodology of the Social Sciences (Max Weber), Forecasting, Time Series, and Regression (Richard T. O'Connell; Anne B. Koehler), Civilization and its Discontents (Sigmund Freud), Brunner and Suddarth's Textbook of Medical-Surgical Nursing (Janice L. Hinkle; Kerry H. Cheever), Chemistry: The Central Science (Theodore E. Brown; H. Eugene H LeMay; Bruce E. Bursten; Catherine Murphy; Patrick Woodward), Give Me Liberty! Theotherquartetcontainingthepeakscentredat3.1ppmand3.7ppm All the reactants were coordinated into complexes which also indicates for a high yield. synthesiscomplexeswithgoodyieldsobtainedaswasanunderstandingof Scheme1Mechanismfortheformationof[Co(diNOsar)]3+ 4Ix#{zwAj}Q=8m The 5, 2018, pp. Esc? The only conditions in which this compound could be formed was by, performing the reaction at a high temperature followed by cooling [2] . Results oxidation the Co(II) ion might due to the Co(II) complex exchanging ligands, Coordination chemistry 1 werners work and werner's theory, Sigmatropic rearrangement reactions (pericyclic reaction), Aromatic Structures and Chemistry of Benzene, Chapter 06 an overview of organic reactions, Conformational analysis of ethane butane aliphatics, B sc_I_General chemistry U-III(A) Alkane,alkene and alkynes, Preparation of potassium trioxalatoaluminate(III) trihydrate. , Mass[Co(diNOsar)]Br3obtained=1.32g The crystals were filtered out with 5ml of dH 2 O followed by 10 ml The equilibrium concentrations must satisfy the following equation: The zinc powder was black in colour while copper (II) sulphate solution was blue in colour because of the presence of copper (II) ions. C C o H 2 N N H 2 8, References Figure4/theelectrochemicalpropertiesof[Co(dinNOsar)3]3+ turned dark blue in pyridine but did not dissolve. CisTrans Isomerization of the [Co(En)2Cl2]+ Complex Ion in Methanol. << /Length 1 0 R /Filter /FlateDecode >> crude product was recrystallized in methanol, a water bath used to quicken the process. Thisindicatesthatinthetwocomplexesthecobaltionis This particular synthesis (6) was a cobalt amine-chloride product. Bain, G. A.; Berry, J. F. Diamagnetic Corrections and Pascals Constants. byusingcyclicvoltammetry. stream Please put it in the container provided, as directed by your instructor. It is extremely soluble. hU`8c#? THE PREPARATION , ANALYSIS AND REACTION OF AN ETHANEDIOATE (OXALATE) COMPLEX photo chemistry of ligand in coordination compound, 17 - Reactions of Aromatic Compounds - Wade 7th. Experimental laboratory manual is intended for students of specialties like Food technology,Technology of processing production, and Biotechnology. fortheconversionofCo(II)backtoCo(III). The lab was also able to determine. metal ion acts by coordinating the reactants5 [Co(en)3]3+ formaldehyde. Kinet. electronicnatureofthemetalion. In this experiment [Co(diNOsar)]Br 3 is synthesised from [Co(en) 3 ]Br 3 in the bandsarefoundtooccuratsimilarwavelengthsforalltwocompounds.The Noticied a slight color change to dark purple. theusefulnessofUVVisandCVininvestigatingcomplexes. Preparation of an Inorganic Cobalt Complex Lab | Lab Reports Chemistry | Docsity, Seminar Assignments - Lab Report For Cobalt Lab. IR spectra for the three products were, This experiment initially involved the synthesis of an iron (III) oxalate complex with the general, Cobalt Complex Project-Synthesis Lab Report, The compounds of the transition metals react with negative ions and/ or neutral molecules to form transition metal complexes.

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