UNIVERSIDADE ESTADUAL DE GOIS

Prof. Dr. Jos Daniel Ribeiro de Campos

Anpolis-GO Fevereiro, 2012

EXPERIMENTOS

Aula 1: Apresentao do curso Aula 2: Sntese do Sulfato de Cobre Pentahidratado (CuSO4.5H2O) Aula 3: Frmula de um Hidrato Aula 4: P1 - Primeira Prova (aulas 2 e 3) Aula 5: Preparao do xido Cuproso (Cu2O) Aula 6: Sntese de Sal Termocrmico tetraiodomercurato de Cobre (I) Aula 7: Reviso Terica das aulas 2, 3, 5 e 6 Aula 8: P2 - Segunda Prova (aulas 2, 3, 5 e 6) Aula 9: A Giant Silver Mirror Aula 10: Preparation and Properties of na Aqueous Ferrofluid Aula 11: P3 - Terceira Prova (Experimentos 9 e 10) Aula 12: Efeito do Nmero de Ligantes sobre a Cor de Compostos de Coordenao Aula 13: Sntese do dioxalatocuprato(II) de potssio diidratado K2[Cu(oxalato)2].2H2O Aula 14: Reviso Terica das aulas 9, 10, 12 e 13 Aula 15: P4 - Quarta Prova (aulas 9, 10, 12 e 13)

CRITRIOS DE AVALIAO
a) Prova escrita Durante o semestre, sero aplicadas 02 (duas) provas escritas (1a e 2a VAs). Nestas provas constaro questes relacionadas com o contedo dos experimentos que as antecedem, ou seja, 1 VA (experimentos de 1 a 5) e 2 VA (experimentos de 6 a 10). O local de realizao das provas ser informado com antecedncia pelo professor. As provas sero avaliadas com notas de 0,0 a 5,0 pontos, ou seja, o correspondente a 50% da nota. b) Relatrios O relatrio de cada experimento ser avaliado com notas de 0,0 a 10,0 pontos. Em caso de ausncia do aluno a nota do experimento ser 0,0 (zero). A mdia dos relatrios ser multiplicada por 0,4, ou seja, correspondente a 40% da nota.

c) Pr-testes Os pr-testes sero aplicados no incio da aula, os quais devero ser feitos no perodo das 7h30 s 7h50. O contedo avaliado ser do experimento a ser realizado no dia. d) Notas Ser avaliado o aproveitamento do aluno mediante acompanhamento contnuo por meio de relatrios, pr-testes e empenho durante a aula experimental, de modo que todo o perodo da disciplina seja oportunidade de avaliao. Essa avaliao ser expressa em graus numricos de zero a dez, computados at a primeira casa decimal. Sero realizadas durante o curso: 4 (quatro) provas tericas, 8 (oito) relatrios em grupos de 3 (trs) alunos e 8 (oito) pr-testes individuais. A nota final (N) ter a seguinte composio final:

Onde, P1 - Primeira Prova (Experimentos 2 e 3), P2 - Segunda Prova (Experimentos 2, 3, 5 e 6), P3 - Terceira Prova (Experimentos 9 e 10), P4 - Quarta Prova (aulas 9, 10, 12 e 13), PtX = pr-testes e RX = relatrios.

Nota final para aprovao ,

Caso a nota seja inferior a esse valor o acadmico precisar fazer a 3 VA. 3 VA = Nota a + Nota da 3 VA 2

Nota final com 3aVA para aprovao ,

CONFECO DO RELATRIO
TTULO: Frase sucinta que indica o principal objetivo da experincia NOME DOS AUTORES: Nomes dos integrantes da equipe que participaram do experimento. INTRODUO TERICA: Descrio da teoria necessria ao entendimento da prtica e da discusso dos resultados. Deve ser uma sntese prpria dos vrios livros consultados. O professor percebe facilmente quando o aluno comea a encher lingia. EVITE RODEIOS. OBJETIVO: Frase sucinta resumindo o que ser feito no experimento. Deve-se usar o verbo no infinitivo. Deve ficar separado da introduo. PARTE EXPERIMENTAL: Descrever o procedimento experimental, ressaltando os principais materiais e equipamentos utilizados na prtica. Deve-se usar o verbo no passado, pois ser descrito o que foi feito no laboratrio. RESULTADOS E DISCUSSO: Consiste na apresentao de todos os dados colhidos em laboratrio ou calculados a partir destes. Alm dos textos explicativos, os resultados podem ser apresentados tambm na forma de tabelas, grficos, etc. Discutir os dados obtidos luz da teoria exposta e comparar com os dados da literatura. A DISCUSSO A PARTE DO RELATRIO QUE EXIGE MAIOR MATURIDADE DO ALUNO. CONCLUSO: Sntese pessoal sobre as concluses alcanadas com o seu trabalho. Enumere os resultados mais significativos do trabalho. REFERNCIAS BIBLIOGRFICAS: Livros e artigos usados para escrever o relatrio. Devem ser indicados cada vez que forem utilizados seguindo as Normas da ABNT NBR 6023/2002. Ex.: No texto: (...) espcies qumicas na superfcie das partculas desestabilizando-as (JAFELICCI JUNIOR e VARANDA, 1999). Bibliografia: JAFELICCI JUNIOR, M.; VARANDA, L. C. O mundo dos Colides. Qumica Nova na Escola, n. 9, p. 9 13, 1999. No texto: (...) radioativos no ofeream riscos sade e rejeio ao consumo (DI BERNARDO et al, 2002). Bibliografia: DI BERNARDO L.; DI BERNARDO A. e CENTURIONE FILHO, P. L. Ensaios de Tratabilidade de gua e dos Resduos Gerados em Estaes de Tratamento de gua. So Carlos: Rima, 2002.

Normas de Segurana para os Laboratrios

Normas Gerais
1. Nunca trabalhe sozinho no laboratrio, caso no seja possvel evitar de trabalhar sozinho, avise o(s) segurana(s) de planto sobre o local onde est e o que fazer em caso de anormalidade; 2. No fume dentro e nem nas imediaes dos laboratrios; 3. No brinque no laboratrio e nem nos corredores de acesso aos mesmos; 4. No beba e nem coma dentro ou prximo aos laboratrios; 5. Todos os produtos qumicos devem ser tratados como venenos em potencial. Caso no se tenha informaes precisas assegurando a sua inocuidade; 6. OBRIGATRIO o uso de avental apropriado (preferencialmente de algodo, longo e mangas compridas); 7. NO SER PERMITIDO o uso de roupas curtas nem calados abertos no laboratrio (minissaias, bermudas, sandlias, etc). O acadmico que no estiver devidamente trajado ser IMPEDIDO de permanecer no laboratrio; 8. Rotule de forma clara, os frascos de acordo com o seu contedo; 9. Use culos de segurana quando estiver trabalhando ou acompanhando um trabalho experimental; 10. Leia com cuidado o rtulo do frasco de reagente para se certificar de que ele realmente o reagente correto; 11. Saiba como operar o chuveiro de emergncia, os lava-olhos e onde ficam os extintores de incndio; 12. Em caso de acidente, comunique imediatamente ao professor responsvel, mesmo que no haja danos pessoais ou materiais aparentes; 13. Nunca use equipamentos de vidro trincados; 14. No use lentes de contato se no estiver devidamente protegido; 15. Caso tenha cabelos longos, prenda-os de forma a evitar acidentes; 16. Caso seja o ltimo a sair do laboratrio, certifique-se que todas as linhas de gases esto fechadas, que as torneiras esto fechadas e que todos os equipamentos estejam desligados, ressalvando aqueles que devem permanecer ligados de forma permanente; 17. Proteja as mos com um pano grosso ao inserir ou retirar hastes tubos e termmetros em rolhas;

18. Verifique com cuidado todas as conexes e ligaes eltricas antes de iniciar uma reao, procura de possveis falhas; 19. Tenha sempre em mente, antes de montar um aparato experimental, os possveis atos que podem levar a um acidente; 20. Lembre-se: vidro quente tem a mesma aparncia que o vidro frio.

Normas Especficas
1. Nunca deixe frascos contendo solventes inflamveis prximos chama ou fonte de fascas eltricas; 2. Nunca deixe frascos contendo solventes inflamveis, especialmente os que contm oxignio em sua estrutura, expostos ao sol; 3. Evite expor a pele ao contato com reagentes qumicos; 4. Use sempre a capela em experimentos nos quais h produo de gases ou vapores; 5. Sempre dilua o cido em gua, nunca o inverso; 6. Nunca pipete lquidos com a boca; 7. Nunca aquea um tubo de ensaio contendo lquido com a boca do tubo voltada para outra pessoa; 8. No jogue reagentes ou produtos de reao na pia sem consultar o professor responsvel; 9. Vidro quebrado deve ser envolvido por vrias camadas de material protetor e descartado em lixeira apropriada; 10. Mantenha a bancada livre de objetos no pertinentes ao trabalho a ser executado; 11. Nunca teste um produto qumico pelo paladar, no caso de teste com o olfato, este deve ser realizado apenas sob orientao do professor responsvel; 12. Em caso de derramamento de reagentes, proceda a limpeza de acordo com a orientao do professor responsvel; 13. Em caso de utilizar um equipamento pela primeira vez, esta deve ser feita sob orientao de pessoa devidamente treinada e qualificada; 14. Mantenha uma distncia segura entre o rosto e os frascos de reagentes, especialmente os novos, antes de abri-los; 15. Use luvas de borracha quando for manipular substncias corrosivas ou txicas; 16. Casos de alergia a produtos qumicos e de gestao (gravidez) devem ser comunicados ao professor responsvel.

Aula 2 Sntese do Sulfato de Cobre Pentahidratado (CuSO4.5H2O) 1. INTRODUO Sulfato de Cobre (II) ou Sulfato Cprico um composto qumico cuja frmula molecular CuSO4. Este sal existe sob algumas formas, que se diferem por seu grau de hidratao. Na sua forma anidra ele se apresenta como um p de colorao verde opaca ou cinzento, enquanto na sua forma pentahidratada (CuSO4.5H2O), a forma no qual mais encontrado, ele azul brilhante. A forma anidra ocorre sob a forma de um mineral raro chamado de calcocianita. A forma hidratada ocorre na natureza como calcantita (pentahidratado). Arcaicamente era chamado de vitrolo azul e pedra-azul. Sulfato de cobre pentahidratado tem ao fungicida. Misturado com cal chamado de calda bordalesa ou mistura de Bordeaux e utilizada para controle de fungos em uvas, meles, e outras frutas. Outra aplicao como composto de Cheshunt, uma mistura de sulfato de cobre e carbonato de amnio, utilizado na horticultura para evitar a queda das plntulas. Seu uso como herbicida no est relacionado com a agricultura, mas sim no controle de plantas aquticas exticas invasivas e razes de outras plantas invasivas prximas a encanamentos contendo gua. A forma diluda do sulfato de cobre usada no tratamento de infeces parasticas em peixes de aqurio, e tambm utilizado para remover caracis de aqurios. De todo modo, como os ons de cobre so extremamente txicos aos peixes, a dosagem deve ser muito bem controlada. A maior parte das espcies de algas pode ser controlada com uma concentrao baixa de sulfato de cobre. Sulfato de cobre inibe o crescimento de bactrias tais como Escherichia coli. 2. OBJETIVOS Sintetizar um sal simples, aplicar as tcnicas de filtrao/precipitao e calcular o rendimento 3. MATERIAIS NECESSRIOS Reagentes 2,0 g de xido de cobre (CuO) 10 mL de cido sulfrico 6 mol/L gua destilada Vidrarias 1 bquer de 100 mL 1 erlenmeyer de 50 mL Funil simples 2 papis de filtro Suporte universal e garras adequadas Funil de Bchner Frasco de Kitassato Bomba a vcuo Banho de gelo

4. PROCEDIMENTO EXPERIMENTAL Sntese 4.1. Pese cerca de 2g de CuO diretamente num bquer de 100ml. 4.2. Em um bquer de 50mL, adicione 5mL de gua destilada e, em seguida 10mL de cido sulfrico 6 mol/L, medidos com uma pipeta graduada, sob agitao e lentamente. 4.3. Transfira lentamente a soluo de cido do bquer para o bquer contendo o CuO. Use uma bagueta de vidro para a transferncia da soluo e agitao da mesma durante a reao. 4.4. Aquea a mistura resultante com placa de aquecimento at dissoluo total do slido. Observe a mudana de cor. 4.5. Deixe a soluo em repouso at que esfrie a temperatura ambiente. Adicione ento mais 5mL de gua destilada soluo e aquea novamente at a ebulio. 4.6. Aps resfriamento da soluo, colocar o bquer em banho de gelo at que no se observe mais formao de cristais. 4.7. Filtre a mistura usando tcnica de filtrao a vcuo. Lave os cristais com etanol gelado at eliminao do cido sulfrico. Obs.: Solte a mangueira do vcuo antes de cada lavagem. 4.8. Seque os cristais durante alguns minutos em estufa 60oC. 4.9. Passe os cristais para um vidro de relgio previamente pesado. Use a bagueta com ponta de borracha para auxiliar a transferncia. Anote a massa e calcule o rendimento. Reao Global: CuO + H2SO4 CuSO4 + H2O

Aula 3 Frmula de um Hidrato 1. INTRODUO Muitos sais, cristalizados a partir de solues aquosas, parecem estar perfeitamente secos, mas quando aquecidos, liberam grandes quantidades de gua. Os cristais mudam de forma, s vezes mesmo de cor, quando a gua lhes retirada, o que indica que a gua estava presente como parte integrante da sua estrutura cristalina. A quantidade molar de gua presentes por mol de sal anidro , normalmente, um nmero simples. A frmula de um hidrato pode ser determinada a partir de uma Anlise Termogravimtrica, sendo obtido um grfico semelhante ao mostrado abaixo para o CuSO.5H2O.

Termograma do CuSO4.5H2O sob vcuo e ar atmosfrico 2. OBJETIVO Determinar a frmula de um hidrato a partir do seu aquecimento. 3. MATERIAL Reagentes 5 g de um dos seguintes hidratos: cloreto de brio (BaCl2.2H2O); sulfato de magnsio (MgSO4.7H2O); carbonato de sdio (Na2CO3.H2O); sulfato de cobre (CuSO4.5H2O); sulfato de mangans (MnSO4.H2O). Equipamentos e vidrarias Balana analtica Bico de Bunsen Cadinho de porcelana Pina de cadinhos Suporte e anel Tringulo Dessecador

4. PROCEDIMENTO EXPERIMENTAL a) Colocar um cadinho limpo e seco num tringulo montado num anel de ferro. Aquecer com uma chama no luminosa durante dois ou trs minutos. b) Quando estiver frio, pesar com uma preciso de 0,01 g. c) Colocar o cadinho no tringulo e aquec-lo. Primeiro suavemente at que a maior parte da gua tenha sido removida, aumentando depois o aquecimento at que o fundo do cadinho fique vermelho escuro. d) Transferir o cadinho para um dessecador. e) Deixar esfriar no dessecador e pesar. f) Aquecer, novamente, o conjunto at ficar vermelho escuro. g) Deixar esfriar no dessecador e pesar. A diferena de massa entre as duas pesagens no deve exceder de 0,02 g. Os dados deverem incluir as seguintes informaes: Peso do cadinho com tampa Peso do cadinho com tampa e o hidrato Peso do cadinho com tampa e o sal anidro (1 pesagem) Peso do cadinho com tampa e o sal anidro (2a pesagem) Peso de 1 mol de sal anidro 5. TRATAMENTO DE DADOS 5.1. Calcule a quantidade molar do sal anidro preparado 5.2. Quantos moles de gua estavam associados com 1 mol da sal anidro? 5.3. Escreva a frmula emprica do sal hidratado. 6. BIBLIOGRAFIA E. M. Lloyd & cols., "Manual de Laboratrio para Qumica Uma Cincia Experimental, 2' edio, Fundao Calouste Gulberkian, Lisboa. g g g g g

Aula 5 Preparao do xido Cuproso (Cu2O) 1. INTRODUO O cobre um dos poucos metais que ocorrem na natureza em estado puro. Na antiguidade era considerado precioso, embora de menor valor que o ouro e a prata. A simplicidade de seu tratamento metalrgico permitiu uma produo elevada j antes do quarto milnio anterior era crist. Desde ento, sofreu progressivas desvalorizaes, at que a telefonia e a eletricidade restabelecessem seu consumo, no incio do sculo XX. Apresenta-se em compostos estveis de valncia 1 (cuprosos) e 2 (cpricos). No atacado pelo ar seco, mas em ar mido que contenha dixido de carbono forma-se uma camada protetora esverdeada de carbonato bsico (azinhavre). Dissolve-se bem no cido ntrico, mas no atacado a frio pelos cidos clordrico e sulfrico; a quente, produz com esses cidos, respectivamente: cloreto cuproso e sulfato de cobre. O cobre forma dois xidos: xido cuproso (Cu2O), e xido cprico (CuO). Ao ar, recobre-se de uma camada de carbonato bsico. o azinhavre. Como esse corpo txico, os utenslios de cobre usados na cozinha devem ser estanhados ou mantidos limpos. Entre os compostos cuprosos, nos quais o cobre univalente, citem-se o xido Cu2O, vermelho, que serve para colorir vidros, e cloreto CuCl, cuja soluo no amonaco reativo do acetileno. Entre os compostos cpricos, mais importantes, nos quais o metal divalente, citem-se o xido CuO, negro, que serve para colorir vidros de verde, e o sulfato CuSO4, azul, empregado na eletrometalurgia, em galvanoplastia, em pintura e em agricultura A reao do sulfito com o oxignio lenta em temperaturas ordinrias e relativamente rpida em temperaturas elevadas. Sais de cobalto e de cobre agem com catalisadores neste processo. A presena de 1 ppm de Cu+2 faz com que 80 ppm de sulfito reajam com 8 a 10 ppm de oxignio em cerca de 5 minutos, ao passo que o tempo de reao reduzido para um minuto, usando-se 0,001 ppm de Co+2, e para 15-20 segundos, usando 0,1 ppm de Co+2. 2. OBJETIVO Preparar o sal cloreto de cobre I e o xido cuproso. Escrever todas as equaes das reaes envolvidas nas snteses. Determinar o rendimento terico. 3. MATERIAL Reagentes Sulfito de Sdio Anidro Cloreto de Sdio Brax Soluo de Sulfato de Cobre 0,4M cido Clordrico Concentrado cido Actico Glacial lcool Absoluto ter Etlico Acetona

Equipamentos e vidrarias Bquer 50 mL Bquer 100mL Bquer 250mL Basto de Vidro Funil de Vidro Papel de Filtro Balana Analtica Bico de Bunsen Trip Tela de Amianto Funil de Decantao Kit para Filtrao a Vcuo 4. PROCEDIMENTO EXPERIMENTAL Soluo A. Em um bquer de 250 mL, prepare uma soluo contendo 3 g de sulfito de sdio e 2,5 g de cloreto de sdio em 20 mL de gua. Coloque esta soluo em uma chapa eltrica e deixe entrar em ebulio Soluo B. Soluo estoque de sulfato de cobre pentahidratado (0,4mol/L) Soluo C. Adicione com uma pipeta 12,5 mL da Soluo B, Soluo A fervente. CuSO4 +Na2SO3 + NaCl CuCl + Na2SO4 CuCl + H2O Cu(OH) + HCl Observar a formao de um fino precipitado esverdeado, que se redissolve quase que imediatamente deixando uma soluo final quase incolor Depois de resfriada a Soluo C, ela deve ser transferida para um funil de decantao e derramada vagarosamente com agitao sobre uma soluo fervente feita com 5g de brax em 100 mL de gua. Forma-se, imediatamente, um precipitado amarelo claro finamente dividido que escurece rapidamente. Na2B4O7 + 7H2O 4H3BO3 + 2NaOH 2Cu(OH) + H3BO3 Cu2O + HBO3- + H2O Deixe a soluo entrar em ebulio e ferver durante 30 minutos. O precipitado depois de agitao se torna cristalino, cor de tijolo. Deixe ento o slido se precipitar, lave com gua fria. Despreze o filtrado inicialmente por decantao. Filtre a presso reduzida e lave o xido formado com alquotas de 1 mL de acetona (3 vezes). Seque ao ar pese at peso constante e determine o rendimento do Cu2O formado. 5. BIBLIOGRAFIA RUSSEL, J. B., Qumica Geral, Trad. de Divo Leonardo Sanioto e cols., McGraw-Hill do Brasil, So Paulo, 1981, Vol. II. LEE, J. D., Qumica Inorgnica- No To Concisa, Trad. Henrique E. Toma e cols., 5a edio inglesa, Editora Edgard Blcher Ltda., So Paulo, 2003.

Aula 6 Sntese de Sal Termocrmico tetraiodomercurato de Cobre (I) 1. INTRODUO O termocromismo um fenmeno associado mudana de cor de uma espcie qumica, no estado slido ou em soluo, na sequncia de uma variao de temperatura. termicamente reversvel e, apesar de a mudana espectral ocorrer geralmente na zona do visvel, pode ocorrer noutra zona do espectro eletromagntico. Este princpio aplicado em situaes do dia-a-dia atravs do uso de materiais termocrmicos tais como os cristais lquidos e as tintas termocrmicas. So exemplos os termmetros (de quarto, de aqurios, de refrigeradores), os brinquedos de banho, os testes de pilhas, as tintas de impresso, os rtulos de produtos txteis e os sensores de temperatura de mquinas industriais. A demonstrao laboratorial proposta tem como objetivo a sntese de uma tinta termocrmica a partir de sais de prata e de cobre que usada como indicador do sobreaquecimento de mquinas industriais 2. OBJETIVO Sintetizar o complexo termocrmico tetraiodomercurato de cobre (II) (Cu2HgI4) 3. MATERIAIS

Soluo de Sulfato de Cobre (II), (0,5 mol/L) Soluo de iodeto de potssio, (1,0 mol/L) Soluo de cido actico, (6,0 mol/L) gua deionizada (ou destilada) Sulfito de sdio Nitrato de Mercrio (0,05 mol/L) Acetona Bqueres de 100 mL e 250 mL Pipetas e/ou provetas (para as medies) Chapa de aquecimento com agitao magntica Im de rotao Filtro de suco Termmetro Conta gotas

3. PROCEDIMENTO EXPERIMENTAL 3.1 Primeiro Passo Adicione 50 mL de gua deionizada em um bquer de 250 mL. Adicione 6mL da soluo de iodeto de Potssio (KI). Em seguida, 5 mL da soluo de sulfato de cobre (II). Por fim, 10 gotas da soluo de cido actico. 3.2 Segundo Passo Pese 0,2 g de Na2SO3 e o dissolva em 10 mL de gua em um bquer de 50 mL. Em seguida, adicione essa soluo ao sistema do primeiro passo, agitando

continuamente. Em seguida, permita que o precipitado de iodeto de cobre "descanse por alguns minutos. Depois disso, separar o sobrenadante do precipitado, perdendo o mnimo possvel do precipitado. OBS.: Usaremos apenas o precipitado 3.3 Terceiro Passo Adicionar a um bquer de 250 mL: 100 mL de gua deionizada; 3,0 mL de iodeto de potssio; 25 mL de Hg(NO3)2 ; adicionar a suspenso do iodeto de cobre,CuI (ppt). Usando uma pisseta, lave o bquer que continha o CuI para remov-lo e adicionlo. Por fim, deve-se aquecer a mistura de CuI e HgI2 at aproximadamente o ponto de ebulio (cerca de 20 minutos) em uma chapa quente sob agitao magntica. Feito isso, ver-se- a formao de um slido marrom escuro. Utilizar um filtro de suco e a mistura ainda quente. Por fim, deixar o slido secar por 10 minutos. 4. EXPLICAO 4.1 Quanto s reaes ocorridas Ao misturarmos a soluo de iodeto de potssio (KI) com o sulfato de cobre (CuSO4) obtemos as seguintes reaes: 2Cu2+(aq) + 4I-(aq) 2CuI(s) + I2(aq) O iodeto de cobre formado pela reduo do cobre pelo iodo, ou seja, o Cu(II) passa ser Cu(I) permitindo sua ligao com um tomo de iodo porm em geral ocorre excesso de iodo nessa reao o que pode formar I3-.Atravs da seguinte reao: I2(aq) + II3-(aq)

O que far com que na soluo haja a primeira equao e: 2Cu2+(aq) + 5I-(aq) 2CuI(s) + I3-(aq)

O problema que o I3- uma agente oxidante o que atrapalha o rendimento da reao (1) que justamente para reduzir o cobre. Assim introduz-se uma soluo de sulfito de sdio (Na2SO3) para que o nion sulfito reduza I3- tornando-o I- : I3-(aq) + SO32-(aq) + 3H2O 3I-(aq) + SO42-(aq) + 2H3O+(aq)

No terceiro passo, fez-se uma soluo atravs da mistura de nitrato de mercrio (Hg(NO3)2) e iodeto de potssio(KI) ocorre a seguinte reao: Hg2+(aq) + 2I-(aq) HgI2(s)

a insolubilidade do HgI2(s) ajuda o equilbrio se manter para a direita. Finalmente o Cu2HgI4 sintetizado pela adio do precipitado da etapa 1 iodeto de cobre (CuI): 2 CuI(s) + HgI2(s) Cu2HgI4(s)

4.2 Quanto a propriedade termocrmica Como foi dito na introduo nosso slido apresenta propriedades termocrmicas. A explicao desse fato encontrada na alternncia das posies dos ons metlicos Hg2+ e Cu+ no estado excitado ou quando lhe so impostos energia cintica devido ao aquecimento. No estado de baixa energia, o slido vermelho caracterstico do arranjo "estacionrio" dos ctions metlicos na "rede" dos tomos de iodeto. Quando no estado de alta energia os ctions apresentam alta movimentao que lhes confere a cor caracterstica, identificada por marrom. Podemos considerar como se houvesse uma mudana do slido em questo, devido a diferena de posicionamento dos ons metlicos nos dois estados. Tambm visto que aps pouco tempo depois de aquecido, o slido rapidamente recupera sua colorao de baixa energia (vermelho), confirmando a diferena entre as estruturas.

Slido no estado de baixa energia

Slido no estado de alta energia

1. Food Classic Chemistry Demonstrations 75

75

Aula 9
THE ROYAL SOCIETY OF CHEMISTRY

32. A giant silver mirror

Topic
The Tollens test for aldehydes and reducing sugars. Also this is an excellent demonstration for general interest.

Timing
About 5 min.

Level
The Tollens test is post-16, but the experiment will fascinate people of all ages.

Description
A solution of ammoniacal silver nitrate is reduced by glucose to silver, which forms a silver mirror on the inside of a large flask.

Apparatus
w w w w w w One 1 dm3 flask with rubber stopper. A round bottomed flask looks most impressive, but any shape will do. One 250 cm3 beaker. Measuring cylinders 25 cm3,100 cm3 and 250 cm3. Dropping pipette. Glass rod. Access to a fume cupboard (optional).

Chemicals
The quantities given are sufficient for three demonstrations. w w w w w w 8.5 g of silver nitrate (AgNO3). 11.2 g of potassium hydroxide (KOH). 2.2 g of glucose (dextrose). 800 cm3 of deionised water. About 30 cm3 of 880 ammonia solution. About 100 cm3 of concentrated nitric acid.

Method
Before the demonstration
Carefully clean the 1 dm3 flask. First use detergent and a brush, then rinse with water, followed by concentrated nitric acid and finally wash it out several times with deionised water. Thorough cleaning is vital if the demonstration is to succeed. Make up the three solutions as follows: w Dissolve 8.5 g of silver nitrate in 500 cm3 of deionised water. This makes a 0.1 mol dm3 solution.

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w w

Dissolve 11.2 g of potassium hydroxide in 250 cm3 of deionised water. This makes a 0.8 mol dm3 solution. Dissolve 2.2 g of glucose in 50 cm3 of deionised water.

The demonstration
Place 150 cm3 of the silver nitrate solution in a 250 cm3 beaker and, working in a fume cupboard if possible, add 880 ammonia using a dropping pipette. A brown precipitate will form. Continue to add the ammonia until the precipitate re-dissolves to give a clear, colourless solution. Less than 5 cm3 of ammonia will be needed. The solution then contains Ag(NH3)2+(aq). Add 75 cm3 of the potassium hydroxide solution. A dark brown precipitate will form. Add more ammonia dropwise until this precipitate redissolves to give a clear, colourless solution. About 5 cm3 of ammonia will be needed. Pour this solution into the 1 dm3 flask and add 12 cm3 of the glucose solution. Stopper the flask and swirl the solution so that the whole of the inner surface of the flask is wetted. The solution will turn brown. Continue swirling until a mirror forms. This will take about 2 minutes. When a satisfactory mirror has formed, pour the solution down the sink with plenty of water. Rinse out the flask well with water and discard the washings down the sink. The flask can now be passed around the class. DO NOT SAVE THE SILVER SOLUTION IN A SILVER RESIDUE CONTAINER. An alternative to plating the inside of a flask is to silver plate the outside of small glass objects which can be suspended in the plating solution by hanging them on threads. These objects must be cleaned beforehand.

Visual tips
The demonstration can be scaled up for greater impact or scaled down for economy.

Teaching tips
This reaction is the well known Tollens or silver mirror test for aldehydes. The method used to be used commercially for silvering mirrors.

Theory
Aldehydes such as glucose are reducing agents and will reduce Ag+(aq) ions to metallic silver. They themselves are oxidised to carboxlyate ions. The reaction that occurs is: CH2OH(CHOH)4CHO(aq) + 2Ag(NH3)2+(aq) + 3OH(aq) 2Ag(s) + CH2OH(CHOH)4CO2(aq) + 4NH3(aq) + 2H2O(l)

Extensions
Try using an ordinary aldehyde instead of glucose, and show that the reaction does not work with a ketone such as propanone.

Further details
The silver can be removed from the silvered flask with concentrated nitric acid. Work in a fume cupboard because nitrogen dioxide is formed. There are reports of silvered flasks being kept for several years as ornaments.

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Safety
Wear eye protection. There have been a few reports of alkaline ammoniacal silver nitrate solutions exploding after standing for some time. This rare occurrence is thought to be caused by the formation of silver nitride or silver fulminate. To avoid this risk, the ammoniacal silver nitrate solution should not be made up before the demonstration and any silvering solution left after the demonstration should not be placed in a silver residues container but should be washed down the sink with plenty of water. The silvered flask should be rinsed thoroughly with water and the washings washed down the sink as soon as the silvering has finished. It is the responsibility of teachers doing this demonstration to carry out an appropriate risk assessment.

In the Laboratory Aula 10

Preparation and Properties of an Aqueous Ferrofluid

Patricia Berger Department of Chemistry, Southern Oregon University, Ashland, OR 97520 Nicholas B. Adelman, Katie J. Beckman, Dean J. Campbell, and Arthur B. Ellis* Department of Chemistry, University of Wisconsin-Madison, Madison, WI 53706; *ellis@chem.wisc.edu George C. Lisensky Department of Chemistry, Beloit College, Beloit, WI 53511

Introduction Imagine the production and applications of a liquid that can be controlled by a magnetic field. Creating a strongly magnetic liquid is not as easy as melting a strongly magnetic solid, since magnetic solids lose much of their magnetism above what is known as the Curie temperature, as thermal energy overwhelms the tendency of their electrons to align in magnetic domains (regions of similarly oriented electron spins). The Curie temperature is well below the melting point for known magnetic materials (13). Ferrofluids, which are colloidal suspensions of magnetic material in a liquid medium, are an example of a liquid that responds to an external magnetic field. The coupling of liquid and magnetic behavior means that the liquids location may be manipulated by an applied magnetic field. Ferrofluids were first developed and classified in the 1960s by Stephen Pappell at NASA as a method for controlling fluids in space (4). NASA initially used them as rotating shaft seals in satellites, and they now serve the same purpose in a wide variety of machines, ranging from centrifuges to computer hard disk drives (1, 2). They are incorporated into the voice coil gap of loudspeakers for damping undesired vibrations and for cooling. Ferrofluids have also been used in the separation of metals from ores by taking advantage of a density change that appears in the fluid under application of a magnetic field. One South African company has even been utilizing ferrofluids to separate diamonds from beach sand (5). In medicine, a ferrofluidic actuator has been proposed for an implantable artificial heart (1). This actuator would be driven simply by applying an external magnetic field. It is possible to attach drugs to the surface of the magnetic particles and use magnetic fields to hold the drug at the site where it is needed (3). Aqueous magnetic fluids have successfully oriented biological assemblies such as the tobacco mosaic virus, enabling information concerning the helical structure of the virus to be obtained (6 ). Recently, ferrofluids have been utilized in conjunction with microcontact printing and capillary filling to fabricate patterned structures of magnetic materials on the micron scale (7 ). The ability to produce patterns of ultrafine magnetic particles has important technological applications, since the information density on tapes, for example, is inversely proportional to the size of the particles. Research has been conducted exploring
Current address: Procter & Gamble de MexicoPDD, poniente 146 #850, Colonia Industrial Vallejo, Mexico DF 02300, Mexico. Current address: Department of Chemistry, Bradley University, Peoria, IL 61625.

Figure 1. Magnetic inks are printed onto paper money for identification purposes. When a strong magnet is brought near a dollar bill (A), the bill is attracted to the magnet (B).

the use of ferrofluids as magnetic inks for ink jet printing (2). Magnetic inks are currently used in printing United States paper currency, as can be demonstrated by the attraction of a genuine dollar bill to a strong magnet (Fig. 1) (8). Background There are two major steps in synthesizing a ferrofluid. The first is to make the magnetic nanoparticles (~100 diameter) that will be dispersed in the colloidal suspension. These particles must be chemically stable in the liquid carrier. The magnetic particles in ferrofluid are generally magnetite, Fe3O4, although other magnetic particles have been used. The second synthetic step is the dispersion of the magnetic particles into a carrier liquid by utilizing a surfactant to create a colloidal suspension. Surfactants are dispersion agents for particles in a liquid that work by adhering to the particles and creating a net repulsion between them (steric and/or coulombic), raising the energy required for the particles to agglomerate, and stabilizing the colloid (Fig. 2) (3). Aqueous-, oil-, and liquid-metal-based (mercury; gallium alloys) ferrofluids have been developed with the proper choice of surfactant (1). The magnetic properties of magnetite that make it a desirable component of ferrofluids are derived from its crystal structure. Magnetite crystallizes in the inverse spinel structure above 120 K (9). The inverse spinel structure consists of oxide ions in a cubic close-packed arrangement. Iron(II) ions occupy 1/4 of the octahedral holes, and the iron(III) ions are equally
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divided between 1/8 of the tetrahedral holes and 1/4 of the octahedral holes. Electron spins of iron(III) ions in octahedral holes are aligned antiparallel to those in tetrahedral holes; therefore, no net magnetization is observed from these ions. The iron(II) ions, however, tend to align their spins parallel with those of iron(III) ions in adjacent octahedral sites, leading to a net magnetization. This arrangement of antiparallel spins throughout the solid that do not completely cancel is referred to as ferrimagnetism. Ferrofluids are actually superparamagnetic, meaning that a ferrofluid reacts to a magnetic field in the same way as a ferromagnetic or ferrimagnetic solid, but magnetizes and demagnetizes more rapidly because in a ferrofluid the magnetic domains are the same size as the actual particles. Manganese and cobalt ferrites, MnFe2O4 and CoFe2O4, respectively, also have the inverse spinel structure and have been used in the preparation of ferrofluids (10). The layer sequences for a conventional cubic unit cell and for a smaller tetragonal unit cell for magnetite are shown in Figure 3. The Fe24O32 cubic unit cell and the Fe12O16 tetragonal unit cell both have the same empirical formula, Fe3O4. Construction directions using the ICE Solid-State Model Kit (11) are included in the Supplemental Material. A cubic unit cell built with the kit is shown in Figure 4. For magnetite to remain in suspension, its particle diameters need to be on the order of 10 nm (100 ) (2, 4b). At room temperature, the thermal energy of these colloidal particles is of the same order of magnitude as the gravitational and magnetic attraction, ~4 10 21 J, and therefore the particles remain suspended. The original ferrofluids developed at NASA used finely divided magnetite, prepared by grinding in a ball mill for several weeks to obtain particles of an appropriate colloidal size. Carrier liquid, surfactant and a dispersant were added during the grinding process to prevent agglomeration of the nanoparticles. In an alternative procedure, as used in this paper, magnetite is synthesized in solution and precipitated as nanoparticles (2, 3). Overview This paper presents an easy, economical method for preparing a ferrofluid that can be used in high school or college science or engineering courses.1 This ferrofluid may be prepared in less than 2 h. The synthesis is based on reacting iron(II) and iron(III) ions in an aqueous ammonia solution to form magnetite, Fe3O4, as shown in eq 1. 2FeCl3 + FeCl2 + 8NH3 + 4H 2O Fe 3O4 + 8NH 4Cl (1) The magnetite is mixed with aqueous tetramethylammonium hydroxide, (CH3) 4NOH, solution. This surfactant can surround the magnetite particles with hydroxide anions and tetramethylammonium cations (12) to create electrostatic interparticle repulsion in an aqueous environment (Fig. 2). This paper also includes a method for applying a ferrofluidresistant coating to objects and describes a dramatic classroom demonstration of the attraction of ferrofluid to magnets. Synthesis

Figure 2. Idealized illustration of an aqueous ferrofliud stabilized by a tetramethylammonium hydroxide surfactant. Surfactant species adhere to the surface of magnetite particles, creating a net repulsion between the particles and stabilizing the colloid. Tetramethylammonium hydroxide can coat the magnetite particles with hydroxide anions, which attract tetramethylammonium cations, forming a diffuse shell around each particle and creating repulsion between particles. The drawing is not to scale.

Figure 3. The layer sequence of magnetite (see ref 4b, Chapter 3, for a discussion of layer sequences). The larger gray square represents the cross-section of the conventional cubic unit cell; the smaller, black-outlined square represents the crosssection of an alternate, smaller tetragonal unit cell. The arrangement of the atoms is the same in both. Fe 3+ is represented by circles of different sizes: large circles represent iron in octahedral coordination, small circles represent iron in tetrahedral coordination.

Safety CAUTION: Gloves and goggles must be worn at all times. Hydrochloric acid and aqueous ammonia are corrosive and should be handled with care. FeCl2 is toxic, corrosive, and a mutagen. FeCl3 is corrosive. Tetramethylammonium hydroxide
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Figure 4. Model of the cubic unit cell of Fe3O4, built with the ICE Solid State Model Kit (11).

is a strong base that is corrosive and flammable. Caution must be exercised when handling any of these materials. Wash immediately with water in case of skin contact. Ferrofluids can be messy. This particular ferrofluid will permanently stain almost any fabric and it has a high pH. It is also very difficult to remove from magnets.

Special Materials Required

Cow magnet (0.5 in. diameter 3 in.), available from farm supply stores or from Edmund Scientific, Barrington, NJ. Strong neodymium-iron-boron (Nd2Fe12B) magnet, available from Edmund Scientific, Barrington, NJ, or Magnet Sales and Manufacturing Company, Culver City, CA. Benchtop centrifuge, such as an International Clinical Centrifuge from the International Equipment Company, Boston, MA. 2.0 M FeCl2 in 2 M HCl (39.76 g of FeCl 2 4H2O in 100 mL of 2 M HCl). 1.0 M FeCl 3 in 2 M HCl (67.58 g of FeCl3 6H2O or 40.55 g of FeCl 3 in 250 mL of 2 M HCl). 0.7 M aqueous NH 3 (48 mL of concentrated aqueous NH3 diluted to 1 L with H2O). 25% aqueous (CH3 )4NOH solution, available from Aldrich, Milwaukee, WI.

NOTE: Stoichiometry of the reaction is important. The solids are hygroscopic and previously unopened reagents will work better. It is absolutely essential that there is no undissolved material in the solutions. Prepare the iron chloride solutions by adding the solid iron chlorides to the 2 M HCl solution. The acidic conditions prevent formation of iron hydroxides. The iron(II) solution is susceptible to air oxidation and should be used within a week of preparation. Both the ammonia and (CH3)4NOH solutions should also be free of undissolved solids. NOTE: We have also found that we can synthesize highquality ferrofluid using 1 M tetra-n-butylammonium hydroxide, also available from Aldrich, in place of tetramethylammonium hydroxide. The ferrofluid spikes are about the same size for both surfactants, but tetramethylammonium hydroxide is less expensive.

then decant and dispose of most of the liquid. Stir the remaining solution and centrifuge the solution for 1 min at 1000 rpm. (In general, at least 1520 mL of liquid should be centrifuged in order to obtain an adequate amount of solid magnetite for preparing a ferrofluid sample; one or more centrifuge tubes can be used for this step, depending on the centrifuge available.) Decant the supernatant after centrifugation. The dark, sludgelike solid at the bottom of the tube is magnetite. Divide 8 mL of 25% tetramethylammonium hydroxide ((CH3) 4NOH) solution among however many centrifuge tubes were used during the centrifugation and stir with a thin glass rod until the solid is completely suspended in the liquid. Pour the contents of all of the tubes into a vacuum filtration flask, add a magnetic stirring bar, and stopper the flask. Magnetically stir the solution under aspirator vacuum for 30 min to remove excess ammonia from the solution. After stirring, slowly pour the liquid into a beaker. The magnetic stirring bar that remains in the filtration flask should be covered with a black sludge, which may or may not exhibit spikes at the ends of the magnet. Gently pour the stirring bar and attached sludge into a plastic weighing boat. Remember that ferrofluids are messy and can easily and permanently stain any fabric. Carefully and slowly hold a strong, block-shaped magnet (preferably a Nd2Fe12B magnetsee above for suppliers) up to the bottom of the plastic weighing boat, keeping it underneath the weighing boat. Using gloved fingers, grasp and rotate the stirring bar about its axis to remove the magnetite adhering to it by allowing the magnetite to be more strongly attracted to the stronger magnet held beneath the weighing boat (Fig. 5). Make sure the magnetite is removed from both ends of the stirring bar. Pull the now-clean magnetic stirring bar out of the weighing boat, being careful not to let it slip back into the weighing boat, where it could cause splashing. With the strong magnet still underneath the weighing boat, pour off any excess water. Finally, carefully remove the strong magnet from the bottom of the weighing boat. Hold a cow magnet up to the bottom of the weighing boat to check whether the ferrofluid forms spikes in the

Procedure Combine 1.0 mL of stock FeCl2 solution and 4.0 mL of stock FeCl3 solution. Place a magnetic stirring bar in the flask and begin stirring vigorously. Add dropwise by pipet or buret 50 mL of 0.7 M aqueous NH3 solution into the flask. We have found that the slow rate of addition is critical, and a pipet or buret is a convenient means of slowing the addition rate. Magnetite, a black precipitate, will form immediately. Stir throughout the addition of the ammonia solution. Cease stirring and allow the precipitate to settle (510 min),

Figure 5. The final ferrofluid preparation step. Remove the magnetite from both ends of the stirring bar by grasping the bar in the center, touching each end in turn to the weighing boat above the strong magnet, and rotating the stirring bar until all of the magnetite adheres to the weighing boat through attraction to the strong magnet beneath the boat.

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groups of students at the beginning of the lab. After the first synthesis is complete, the resulting fluids can be checked for spiking with a magnet. The stoichiometric ratio that results in the best ferrofluid (the one that responds most dramatically to a magnet) can then be assigned to the entire class for a second ferrofluid synthesis, allowing everyone to prepare a highquality ferrofluid. The structure of the synthesized magnetite particles can be identified by X-ray powder diffraction. The average particle diameter for the crystalline precipitate can be determined by Scherrers formula, eq 2, using the half-widths of the most intense X-ray diffraction peaks (3, 13).
Figure 6. A side view of the spiking effect of an aqueous-based ferrofluid in the presence of a cow magnet, which is placed underneath a weighing boat.

t = (0.9 )/(B cos B)

(2)

presence of a moderate magnetic field (Fig. 6) (a more detailed description of ferrofluid spiking is given in the Results and Discussion section). If the fluid does not spike, or the spikes are small, remove the cow magnet, add one drop of distilled water, stir well with the glass rod, and again check for spiking with the cow magnet. If spikes are still not seen, try adding one or two more drops of water. It should not take more than a few drops to obtain a good spiking effect. If too much water is added, the ferrofluid will become too dilute and will not spike. If the ferrofluid is too dilute, hold the strong magnet under the weighing boat, then tilt the weighing boat so that the excess liquid runs off. Results and Discussion A fascinating physical property of a ferrofluid is the unusual distortion that the fluid experiences when exposed to a magnetic field. When a high-quality ferrofluid is brought into contact with a moderate magnetic field, such as that from a cow magnet, it develops spikes on its surface (Fig. 6). These spikes, which may adopt a close-packed hexagonal pattern, are due to surface instability of the suspended particles. The surface instability associated with the ferrofluid causes small waves to be constantly present on the surface of the liquid (2). When a magnetic field is applied, the amplitude of the waves increases until they begin to form peaks. If the magnetic force is large enough to dominate the forces of surface tension and gravity, the spikes appear. The spikes increase in size as the magnetic field is increased. By far, this is the easiest and most fascinating test for a high-quality ferrofluid. However, if the magnetic field becomes too great, the magnetic particles will reversibly precipitate from the solution (3). The synthetic procedure described above can be carried out with varying mole ratios of FeCl2 to FeCl3 in order to demonstrate the effect of stoichiometry. About 250 pairs of undergraduates in an introductory chemistry lab performed the synthesis with varying ratios of the precursor iron chloride solutions. There was time during the three-hour lab period for the students to perform the synthesis with the 2:1 iron(III)/ iron(II) stoichiometric ratio that is known to work, as well as a second synthesis using a different stoichiometric ratio. A graph of the percent of successful syntheses (ferrofluids that spiked) as a function of precursor solution ratios for the pooled student data is shown in Figure 7. An alternate format for the lab is to assign different stoichiometric ratios to different
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In this formula, t is the particle diameter in , is the wavelength of the X-ray radiation in , B is the Bragg angle ( ) of the peak, and B is the peak broadening. Peak broadening is a measure of the size of the nanoparticles with respect to reference particles. The reference particles must have a crystal thickness greater than ~2000 , which gives relatively narrow peaks (Fig. 8A). A commercially manufactured sample of magnetite has particles that are sufficiently large to serve as a reference. The peaks for the colloidal sample are typically broader (Fig. 8B). The peak broadening, the difference between the sample and reference peak widths, is given by the Warren formula (eq 3) (14).
2 2 B 2 = Bcolloid sample B bulk material

(3)

B is the peak width (in radians) that is measured at half the maximum peak intensity. The data for the bulk material may be obtained from JCPDS files (15) or from a diffraction pattern of commercial Fe3O4 (available from Aldrich, Milwaukee, WI) having an average crystal size greater than ~2000 (13). Using the peak at 2 = 35.6 (Miller indices, (311)), the average size of magnetite particles synthesized by the method described in this paper is ~14 nm.2 These magnetite particles are small enough to sustain a colloidal suspension, and a good ferrofluid can be produced.

Figure 7. Percent success of the ferrofluid synthesis as a function of iron chloride solution mole ratios for a group of ~250 pairs of undergraduates performing the experiment during the third week of class. Most of the trials were conducted with the 2:1 Fe3+/Fe 2+ ratio.

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A Ferrofluid-Resistant Coating Many water- and oil-based ferrofluids tend to stain (sometimes permanently) materials with which they come into contact. This procedure outlines a method to affix a ferrofluidresistant coating to a container. (The container should be able to withstand temperatures in the range of 120180 C.) Scotchgard Fabric Protector FC-247 is a concentrated aqueous suspension of fluoroaliphatic resin; it can be obtained from 3M Specialty Chemicals Division, St. Paul, MN. Avoid eye and prolonged skin contact with this suspension. Thoroughly coat the surface of the container that will contact the ferrofluid with the Scotchgard: rotate the vessel or use a spray-bottle to evenly coat it, then pour out the excess liquid. (The excess can be poured back into its storage bottle to be reused.) Allow the container to dry for approximately an hour

in open air, then place it in a 120180 C oven for 30 min. Let the vessel cool to room temperature before allowing ferrofluid to contact the treated surface. We have found this coating to resist wetting and staining by ferrofluid for a period of several weeks. This coating can be removed by soaking in hot soapy water or a KOH/isopropanol base bath. Scotchgard fabric protector, sold in spray cans, provides a more limited resistance to ferrofluid. The Leaping Ferrofluid Demonstration The following describes a demonstration (Fig. 9) that uses magnets to force a ferrofluid to leap into the air, providing a dramatic demonstration of the effects of magnetic fields on ferrofluid. Using a cork borer, bore a hole slightly smaller than the diameter of an 18 130-mm test tube (~17 mm) in a #13 rubber stopper, then push the test tube through the hole until the stopper is about a third of the way from the bottom of the tube. This stopper will prevent ferrofluid from following the magnets all the way up the test tube. Attach a 3-fingered clamp near the bottom of a ring stand and place the test tube vertically in the clamp, leaving about 3 cm clearance under the end of the test tube. Stack small strong magnets so the poles are at the ends of the stack. Nd2Fe12B magnets, such as those available from Edmund Scientific Corporation, Barrington, NJ, or Magnet Sales and Manufacturing Company, Culver City, CA, work well, as long as they are sufficiently small to fit easily into the test tube. Tie the end of the string around one of the magnets. Place the tied magnet on one end of the stack, using broken magnet pieces (broken with a hammer) as spacers to give more stability to the gap caused by the string (Fig. 10). Attach a ring clamp near the top of the stand, thread the string through a one-hole #1 rubber stopper that will be placed in the open end of the test tube (small side of the stopper toward the magnets) and through the ring clamp ring, and tie the other end to a ~100-g weight. The weight should be slightly heavier than the magnets, so that Figure 10. Construction when it is released it will hold the of the magnet stack used magnets in the up position, away in the leaping ferrofluid from the ferrofluid that will be demonstration. placed below the test tube. Place the magnets in the test tube and fill the tube with mineral oil to about 2 cm from the top. The viscous oil decreases the descent rate of the magnets, preventing splashing of the ferrofluid from the external walls of the glass tube. Apply silicone caulk to the mouth of the tube and to the sides of the small stopper, then insert the stopper and cure for 24 h. A watch glass with a small amount of ferrofluid (a few milliliters of either a commercial oil-based ferrofluid from Ferrofluidics Corporation, Nashua, NH, or the water-based ferrofluid synthesized using the procedure given in this paper) can then
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Figure 8. (A) X-ray powder diffraction pattern of commercially available magnetite. (B) X-ray powder diffraction pattern of the magnetite synthesized by the technique outlined in this paper. Using eqs 2 and 3, the average particle size is about 14 nm. The peak used in the calculations was at 2 = 35.6 (Miller indices, (311)). The asterisk indicates an impurity peak.

Figure 9. Construction of the leaping ferrofluid demonstration.

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(DMR-9632527) for generous support of this research. We also thank Judith Burstyn for use of her supercentrifuge, Joel Miller for informing us of the magnetic inks in paper currency, and John Zhang and David Larbalestier for helpful discussions of magnetic phenomena. We thank Karen Nordell and S. Michael Condren for help with the synthesis, and Lawrence F. Dahl, Douglas R. Powell, and Mikhail Khoudiakov for assistance in the X-ray diffraction measurements. We are grateful to Patrick Doolan, the UW-Madison General Chemistry staff, and the 1997 UW-Madison Chemistry 109 class for assistance in refining the ferrofluid synthesis. Notes
Supplementary materials for this article are available on JCE Online at http://jchemed.chem.wisc.edu/Jour nal/issues/1999/Jul/ abs943.html and can be downloaded from this site. ffsup is a Microsoft Word 6.0 document of instructions for building the solid state model of the magnetite structure and the student laboratory synthesis of ferrofluid. Images and movies of these and other experiments are available at the Materials Research Science and Engineering Center for Nanostructured Materials and Interfaces Education and Outreach Web site, http://mrsec.wisc.edu/edetc/. 1. A classroom kit (The Ferrofluidic Adventure Science Kit) is available from Ferrofluidics Corp., 40 Simon St., Nashua NH 03061; phone: 603/883-9800; fax: 603/883-2308; www.ferrofluidics.com. 2. Experimental conditions for powder diffraction: Scintag PAD V diffractometer, Scitag Inc., Cupertino, CA; X-ray source: = 1.540562 (Cu 1KLIII); steptime: 0.600 s; stepwidth: = 0.020, 2 = 0.040; 2 range: 20 70; scan rate: 20/min
W

Figure 11. The leaping ferrofluid demonstration. (A) The magnets are in the raised position. (B) The magnets are in the lowered position. (C) Ferrofluid spiking at the end of the test tube, which occurs when the magnets are in the lowered position.

Literature Cited be placed under the test tube. An option to prevent staining and to aid draining of ferrofluid off of the tube is to treat the contact surface of the test tube (that below the large rubber stopper) and of the watch glass with Scotchgard (see above). When the weight is lifted, lowering the magnets through the oil, the ferrofluid leaps to the surface of the test tube, displaying its dramatic spiking (Fig. 11). When the weight is lowered, the magnets are raised, pulling the ferrofluid along with them until they are prevented from following any farther by the barrier of the large rubber stopper. At this point the ferrofluid drains off the test tube back into the watch glass. If the ferrofluid does not leap to the magnets, the test tube should be moved closer to the ferrofluid. The demonstration may be repeated many times successively and presented in a large lecture hall using a video camera. Conclusion Ferrofluids are fascinating materials. They are easy to synthesize and the preparative procedures illustrate a wide variety of chemical and physical concepts, including stoichiometry, crystal structure, colloidal properties, oxidation states, and magnetism. The small size of the particles also provides a means for introducing nanoscale materials and preparation. The synthesis and properties of ferrofluids would fit into the curriculum of many types of introductory science and engineering laboratory courses. Acknowledgments We would like to thank the National Science Foundations REU Program and the Materials Research Science and Engineering Center for Nanostructured Materials and Interfaces
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1. Popplewell, J.; Charles, S. New Sci. 1980, 87(1220), 332. 2. Rosensweig, R. E. Scientific American 1992, 247(4),136. 3. Magnetic Fluids and Applications Handbook; Berkovski, B., Ed.; Begell House: New York, 1996. 4. (a) Papell, S. S. Low Viscosity Magnetic Fluid Obtained by the Colloidal Suspension of Magnetic Particles; U.S. Patent 3 215 572, Nov. 2, 1965. (b) Ellis, A. B.; Geselbracht, M. J.; Johnson, B. J.; Lisensky, G. C.; Robinson, W. R. Teaching General Chemistry: A Materials Science Companion; American Chemical Society: Washington, DC, 1993; Chapter 2; (now available from Oxford University Press). 5. Ogden, F. The Last Book Youll Ever Read; MacFarlane, Walter, and Ross: Toronto, 1993; p 206. 6. Sosnic, T.; Charles, S.W.; Stubbs, G.; Yan, P.; Bradbury, E. M.; Timmons, P.; Trewhella, J. Biophys. J. 1991, 60, 1178. 7. Palacin, S.; Hidber, P. C.; Bourgoin, J.; Miramond, C.; Fermon, C.; Whitesides, G. Chem. Mater. 1996, 8, 1316. 8. Trade 2000. Counterfeit Money Detector; http://www.trade2000. com/intro.htm (accessed Mar 1999); this Web site describes a device that examines paper currency by checking for the presence of magnetic ink. 9. Hyde, B.G.; Andersson, S. Inorganic Crystal Structures; Wiley: New York, 1989. 10. Tourinho, F. A.; Franck. R.; Massart, R. J. Mat. Sci. 1990, 25, 3249. 11. Mayer, L. A.; Lisensky, G. C. Solid-State Model Kit; Institute for Chemical Education: Madison, WI, 1993. University of Wisconsin Madison Materials Research Science and Engineering Center; Instructional Materials; http://mrsec.wisc.edu/edetc/; accessed May 1999. 12. Jolivet, J. P.; Massart, R.; Fruchart, J. M. Nouveau J. Chim. 1983, 7, 325. 13. Nuffield, E. W. X-ray Diffraction Methods; Wiley: New York, 1966. 14. West, A. R. Solid State Chemistry and Its Applications; Wiley: New York, 1995; p 175. 15. JCPDS file 19629; Joint Committee on Powder Diffraction: Swarthmore, PA.

Journal of Chemical Education Vol. 76 No. 7 July 1999 JChemEd.chem.wisc.edu

Aula 12 Efeito do Nmero de Ligantes sobre a Cor de Compostos de Coordenao 1. INTRODUO Em qumica de coordenao, o termo complexo significa um tomo metlico ou on central rodeado por um conjunto de ligantes. Um ligante um on ou molcula que pode ter existncia independente. Exemplo de um complexo o [Co(NH3)6)]3+, no qual o on Co3+ est rodeado por seis ligantes NH3. O termo composto de coordenao usado para designar um complexo neutro ou um composto inico no qual pelo menos um dos ons um complexo. Um complexo a combinao de um cido de Lewis (o tomo metlico central) com vrias bases de Lewis (os ligantes). Os ligantes podem ser classificados conforme o nmero de tomos ligados ao on metlico. Ligantes que se coordenam atravs de um tomo so chamados de monodentados. Ligantes que possuem mais do que um ponto de ligao so chamados como polidentados. Os ligantes que se coordenam atravs de dois tomos so chamados de bidentados, aqueles com trs, como tridentados e assim por diante. Um exemplo o ligante bidentado etilenodiamino (en, NH2CH2CH2NH2), que forma um anel de cinco membros quando os tomos de N se ligam ao mesmo tomo metlico. Quando os dois nitrognios efetuam ligao coordenada para um mesmo tomo metlico, o ligante dito quelante e o complexo pode ser chamado de quelato. Quando cada um dos nitrognios efetua uma ligao coordenada para um tomo metlico distinto (estes metais podem ser iguais ou diferentes), a ligao dita em ponte. 2. OBJETIVO Estudar o efeito do nmero de ligantes sobre a cor de complexos de nquel. 3. EXPERIMENTAL 1. 2. 3. 4. Prepare 200 mL de uma soluo aquosa 0,2 molar de cloreto de nquel. Prepare 1 L de uma soluo aquosa 0,2 molar de etilenodiamina. Coloque 5 mL da soluo de cloreto de nquel em trs bqueres de 50mL. Acrescente, ao primeiro bquer, 5 mL da soluo de etilenodiamina, ao segundo 10 mL e ao terceiro 15 mL da mesma soluo. 5. Anote as cores observadas. 6. Quais concluses podem ser obtidas com base nos resultados observados? Quais os produtos formados em cada caso? Lembre-se que a etilenodiamina um ligante bidentado e que o Ni2+ pode formar compostos com nmero de coordenao 6. 7. Tome aproximadamente metade de cada uma das solues formadas no passo 4 e acrescente, a cada uma, gota a gota, cido clordrico concentrado, at que a cor original da soluo de cloreto de nquel tenha sido restabelecida.

4. QUESTES 1. Em qual caso foi necessrio utilizar mais cido? Por qu? 2. Quais concluses podem ser obtidas a partir desses dados experimentais?

Aula 13 Sntese do dioxalatocuprato(II) de potssio diidratado K2[Cu(oxalato)2].2H2O1* 1. INTRODUCTION The oxalate anion is capable of acting as a bidentate chelating agent1 and forms fivemembered rings with many metal ions. A simple, rapid preparation resulting in a high yield of the potassium salt of a copper (II) complex containing this chelating anion is presented which is a modification of a method used for the sodium salt.2 All the chemicals used were of reagent quality. 2. PROCEDURE A solution of 2.5 g. (0.01 mol) of copper(II) sulfate 5-hydrate dissolved in 5 ml of water is heated to 90 and is added rapidly and with vigorous stirring to a solution of 7.36 g (0.04 mol) of potassium oxalate 1-hydrate in 20 ml of water which is at 90. The solution is then cooled to 10 in an ice-water bath and the resulting precipitate is filtered, washed rapidly with 5 ml of cold water, and dried in an oven at 50 for 30 minutes. The yield is 17.1 g. (97%). Anal. Calcd. for K2[Cu(C2O4)2].2H2O: C, 13.58; H, 1.14; K, 22.10. Found: C, 13.78; H, 1.05; K, 22.48. 3. PROPRIETIES The compound is soluble in warm water but begins to decompose slowly into copper(II) oxalate, which precipitates shortly after dissolution of the complex. The decomposition is hastened by the addition of strong acid. The material is only very slightly soluble in the common organic solvents such as acetone, benzene, carbon tetrachloride, chloroform, ethanol, and methanol. The blue crystals lose water rapidly above 150 and the resulting compound decomposes at 260. 4. REFERENCES 1. A. E. Martell and M. Calvin: "Chemistry of the Metal Chelate Compounds," p. 66, Prentice-Hall, Inc., Englewood Cliffs, N.J., 1952. 2. H. L. Riley: J. Chem. Soc., 1929, 1307.

1*

ROCHOW, E. G. (ed.). Inorganic Syntheses. vol. VI, New York, McGraw Hill. pg. 1(1960).