氢、碱金属和碱土金属课件

单击此处编辑母版标题样式,单击此处编辑母版文本样式,第二级,第三级,第四级,第五级,*,中国科学技术大学化学系,中国科学技术大学化学系,单击此处编辑母版标题样式,单击此处编辑母版文本样式,第二级,第三级,第四级,第五级,*,中国科学技术大学化学系,单击此处编辑母版标题样式,单击此处编辑母版文本样式,第二级,第三级,第四级,第五级,*,中国科学技术大学化学系,单击此处编辑母版标题样式,单击此处编辑母版文本样式,第二级,第三级,第四级,第五级,*,氢、碱金属和碱土金属,Hydrogen , Alkali and Alkali-earth metals,氢、碱金属和碱土金属 Hydrogen , Alkali,1,氢及其化合物（,Hydrogen ant its compounds,）,氢在周期表中排,A,，又能排,A,，这是由于第一周期的稀有气体电了构型为,1s,2,。,一、单质氢（,Simple substance of hydrogen,）,1,、氢的同位素（,isotope,）,(1),P P+n P+2n,Protium Deuterium Tritium,氕 氘 氚,1氢及其化合物（Hydrogen ant its comp,(2),存在,：,H:D=6800:1(,原子个数,) H:T=1e10:1,Heat,Cool,(2)存在：H:D=6800:1(原子个数) H:T=,(4),氢同位素形成的单质,H,2,、,D,2,、,T,2,在化学性质上,完全相同，但物理性质（熔沸点）上有差别。,2. Properties:,(1) Physical properties:,H,2,：极难溶于水和有机溶剂，可以贮存在金属,(Pt,、,Pd),和合金,(LaNi,5,),中,固态氢（黑色）又称为金属氢：在晶格质点上为质子，而电子为整个晶体享，所以这样的晶体具有导电性，固态氢可能为立方或六方分子晶格。,(4) 氢同位素形成的单质H2、D2、T2,在化学性质上,(2)Chemical properties:,a.,成键特点：电子构型为,1s,，可以放在,A,类，,但第一电离势高于碱金属的第一电离势；也可放在,A,类。,b.,化合反应：与金属,: 2Na + H,2,= 2NaH,Ca + H,2,= CaH,2,与非金属,: H,2,+ F,2,= 2HF,c.,还原反应：,CuO + H,2,= Cu + H,2,O,WO,3,+ 3H,2,= W + 3H,2,O,(2)Chemical properties:,3.Preparation,(1),实验室：,(2),工业上：,二、氢化物（,Hydride,）放在以后各章元素中讲解,http:/www.chemsys.t.u-tokyo.ac.jp/laboratory_domen-kubota_e.html,Si(s) +Ca(OH),2,(s) +2 NaOH (s) = Na,2,SiO,3,(s) +CaO (,?,)+ 2H,2,(g),3.Preparation二、氢化物（Hydride）放在,2,碱金属元素及其化合物,Alkali metals and their compounds,Lithium Sodium Potassium,Li Na K,Rubidium Cesium Francium,Rb Cs Fr,2碱金属元素及其化合物,for structural and mechanistic studies of ion channels,Roderick MacKinnon,The Nobel Prize in Chemistry 2003,Peter Agre, Roderick MacKinnon,K,+,channel,for structural and mechanistic,氢、碱金属和碱土金属课件,氢、碱金属和碱土金属课件,氢、碱金属和碱土金属课件,I was born on February 19, 1956 in the middle of a snowstorm. It remains one of those humorous family stories that my mother likes to tell. My father the planner had rehearsed the way to the hospital but apparently things looked a lot different at night in a blizzard. Eventually they made it and so did I, the fourth of seven children. My father was a postal worker when I was very young but studied computers and became a programmer on the big IBM main frames. My mother worked as a part time schoolteacher, but mostly took care of the children at home. Thinking back on it now I know we did not have much money but I never knew that growing up. My parents provided a happy environment and made their expectations clear to us. Television is bad for you, reading is good for you, and you better get an A for effort in school. What you end up doing in life is up to you. Just make sure you enjoy what you do because then you will do it well. We all pursued completely different walks of life. I became the scientist.,I suppose there were some early indications of my tendency to a life of curiosity. Apparently from a very young age I had a habit of asking lots of questions: what would happen if.? was a favorite. And I liked having facts straight and knowing how things work and did not hesitate to give explanations to those around me, apparently to an annoying degree sometimes. I remember one day my father, at the end of his patience, commenting that I was a compendium of useless information. I certainly can understand his plight with one of the seven having way too many questions and answers all the time. On the positive side, I learned a new word that day when I looked up compendium in the dictionary.,There were probably even indications that my curiosity might be scientific. Burlington Massachusetts was rural when I was young and I loved to roam and explore. I had rock collections and read childrens books on geology and the history of the earth. I made little volcanoes out of plaster of paris and added baking soda and vinegar to the craters to simulate volcanic eruptions. I had an accident one day that made my mother laugh to my utter frustration: at that young age I failed to appreciate the humor in a little boy telling his mother he had dropped a volcano on his toe! In the summer I collected butterflies, turtles, snakes and other living things. One summer my mother enrolled me in a science enrichment class for elementary school students and I was allowed to take home a microscope. I used it to look at everything I could find: microorganisms from the nearby pond, leaves and blades of grass. I spent hour after hour alone, mesmerized by the tiny little things that I could see.,I was born on February 19, 195,My scientific curiosity took a back seat to athletics through junior high and high school. Gymnastics was a good match to my small build and to my solitary nature. I was a member of a team but gymnastics is an individual sport. You learn a technique, then a move, and then a routine. And then you perfect it through practice, working mostly alone. I had a very good no nonsense teacher, coach Hayes, who really instilled in me the idea of perfection through practice. I was actually not all that bad, particularly at floor exercise and high bar. I even considered pursuing gymnastics in college, but during my final year of high school I began to wonder what I should pursue for a career.,I attended the University of Massachusetts in Boston for one year and then transferred to Brandeis University. Brandeis was an eye opening experience for me. For the first time in my life I was in a seriously intellectual environment. The classes tended to be small, intense, and stimulating. I discovered that I had a passion for science, and that I was very good at it. I chose Biochemistry as a major and a newly arrived assistant professor named Chris Miller for my honors thesis advisor. He had a little laboratory with big windows and lots of light shining in. I studied calcium transport and learned about the cell membrane as an electrode. I could see that Chris Miller was a man having lots of fun in his daily life and it was inspiring to me, and the memory of this stayed with me. But the biggest influence Brandeis had on my life happened in Physics class. There I met my future wife Alice Lee, whose sparkling eyes and sharp mind caught my attention.,Against Chris Millers advice I went to medical school after Brandeis. I studied at Tufts University School of Medicine and then at Beth Israel Hospital Boston for house officer training in Internal Medicine. I learned a lot but in the end I should have taken Chris advice to pursue science. Medicine required a lot of memorization and little analytical problem solving. To keep a certain part of my brain active I began to study mathematics, and continue this even today, learning new methods and solving problems with the same disciplined approach I had learned in gymnastics. I started back to science near the end of house officer training working with Jim Morgan studying calcium in cardiac muscle contractility, which was very enjoyable and kept me connected to medicine. But I had a yearning to work on a very basic science problem, which meant I would have to break my medical ties. This was a difficult decision because I had invested so many years in medical education; to abandon it was to admit to myself that I had misspent a big piece of my life. And there were practical considerations as well. It was time finally to get a permanent job; after all, my wife Alice had supported me through years of training. Not to mention I was nearly 30 years old with no real basic science training beyond my Brandeis undergraduate education: would I even be able to make it as a scientist?,My scientific curiosity took a,Two factors had the greatest influence on my decision. Back in my first year of medical school I lost my sister Elley, an artist only two years my senior. Diagnosed with leukemia during my hematology clerkship as I learned about the dreaded disease, she lasted only two months. This horrifying event impressed upon me how fragile and precious life is, and how important it is to seize the moment and enjoy what you do while you can. I remember thinking when I look back upon my life at the age of seventy, thirty will seem young: just go for it. And the second factor was Alice. She had complete faith in my ability to succeed. Never mind that postdoctoral studies meant a reduction of my already piddling house officer salary. She simply said you have no choice; we will manage somehow.,Memories of Chris Millers laboratory beckoned so I returned for postdoctoral studies. Of course I will never out live his reminding me that I should have listened to him in the first place. Feeling far behind in my knowledge I approached my postdoctoral studies with intensity, learning techniques and theory. I felt I should be an expert in electrochemistry, stochastic processes, linear systems theory, and many more subjects. I read books, solved the problem sets, mastered the subjects, and carried out experiments. I had the very good fortune of a coworker Jacques Neyton, a postdoctoral scientist from France. Jacques is a very critical thinker who would brood on a problem. We exchanged ideas often. When I would tell him one of my ideas he had a tendency just to listen quietly. Then, after a while, if his response started with Hey Roddy, theres something I dont understand I knew I was in trouble - my idea was probably no good!,After I completed a series of biophysical studies on K+ channels it came time to apply for an academic position. During the late 1980s physiology departments were more interested in hiring channel gene cloners than bio-physicists. But Peter Hess convinced his colleagues at Harvard that my work showed promise and I was offered an assistant professorship there. My laboratory made good progress on K+ channels. It was exciting for a while but in just a few years I began to feel that the return on what we could learn from studying the functional effects of mutations was diminishing. We had identified the K+ channel signature sequence, but without knowing its structure we never would understand the chemical principles of ion selectivity in K+ channels. I decided at that point to learn X-ray crystallography to someday see a K+ channel.,Two factors had the greatest i,I began to learn methods of protein purification and X-ray crystallography while still at Harvard, initially working with channel toxins and a small soluble protein called a PDZ domain. However, I thought it best to move away from my familiar environment at Harvard to pursue channel structure. There were really two reasons motivating me to move. First was the practical issue of obtaining funding to work in an area in which I had no background: start-up funds associated with moving to a new university would be useful for this purpose. The second and far more important reason was that moving would enable me to immerse myself completely in the new endeavor. A change of environment would remove the distractions of everyday life, isolate me from the temptation to fall back on channel physiology studies that I was already good at, and allow me to focus with singular purpose on the structural studies. I needed this to become an expert in membrane protein biochemistry and X-ray crystallography, and to develop a feel for protein structure. When the president of Rockefeller University,Torsten Wiesel,heard about my scientific plans he suggested that I move to Rockefeller University and I did. Rockefeller provided a wonderful environment for concentrating on a difficult problem.,It has been said that giving up my already successful lab at Harvard in order to pursue the structure of a K+ channel was a risky thing to do. At the time I was told that my aspirations were altogether unrealistic. From my perspective I had little choice because I wanted to understand K+ selectivity and I knew that the atomic structure provided the only path to understanding. I would rather fail trying than never try at all. It helped that I was accustomed to making transitions and had become good at teaching myself new subjects. I have to admit that few people working with me at the time wanted much to do with the new endeavor - only one new postdoctoral scientist Declan Doyle was enthusiastic. My wife Alice, an organic chemist, saw that I was going to be pretty lonely and decided to join me in the lab. And to my good fortune she has worked with me since. I have learned that most people do not like change but I do. For me change is challenging, good for creativity, and it definitely keeps life interesting.,I began to learn methods of pr,I think of the past eight years of my life in New York at Rockefeller University as a personal odyssey. The new laboratory started out very small, with only Declan, Alice and me. But it grew in the first year with the addition of other enthusiastic postdoctoral scientists, including Joo Morais Cabral and John Imredy. Working with membrane proteins was very difficult as expected. We had our periods of despair, but every time we felt left without options something good happened and despair gave way to excitement. Persistence and dedication eventually paid off. The atomic structure of the K+ selectivity filter was more informative and more beautiful than I ever could have imagined. My laboratory now is an incredible place, overflowing with excitement and ideas sustained by the continual infusion of bright young scientists who come from around the world to work with me. It gives me great satisfaction to know that these young scientists who are sophisticated in their knowledge of protein chemistry and structure will lead the field of ion channel research into the future. This has been a wonderful adventure. I owe thanks for the life I have: to Alice, to all my loving family of MacKinnons and Lees, to my scientific family of students, postdocs and colleagues, to senior colleagues who have helped me along my way to pursue my passion, and to the Rockefeller University, the Howard Hughes Medical Institute, and the National Institutes of Health for their support. I am very thankful for my life as a scientist, for the opportunity to understand in some small way the world around me. I hope my best experiment and scientific ideas are yet to come. This hope keeps me going.,http:/www.nobelprize.org/nobel_prizes/chemistry/laureates/2003/mackinnon.html,I think of the past eight year,一、,General properties,1. Valence electron of alkali metals:,(1),其氧化数为,+1,，不会有其它正氧化态。,在无水无氧条件下，可以制得低氧化态的非,寻常化合物。例如钠在乙二胺和甲胺中所形,成的溶液也具有导电性，观察到,Na,-,的光谱,带，说明主要的导电体应是钠电离出的,Na,+,和,Na,-,。,cryptand-222,一、General propertiescryptand-,Inverse sodium hydride,+ H,2,Inverse sodium hydride+ H2,(2),由于价电子数少，所以碱金属原,子之间的作用力比绝大多数其他金属,原子之间的作用力要小，因此碱金属,很软，低熔沸点，且半径大、密度小。,Li,的密度是所有金属中最小的，它的,密度比煤油小。,(2) 由于价电子数少，所以碱金属原,2.,在形成化合物时，碱金属元素以离子键,结合为特征，但也呈现一定程度的共价性。,(1),气态双原子分子,Na,2,、,Cs,2,以共价键结合,(2) Li,的一些化合物共价成份最大，从,Li,Cs,的化合物，共价倾向减小。,2. 在形成化合物时，碱金属元素以离子键,(3),某些碱金属的有机物，有共价特征。,例如,Li4(CH3)4,甲基锂,(3) 某些碱金属的有机物，有共价特征。,氢、碱金属和碱土金属课件,二、,Lithium and its compounds,1. General properties:Li,的性质与碱金属有很大区别，但与碱土金属，特别是,Mg,的化学性质相似，这种关系称为对角线关系（,diagonal relationship,）。,Li,与碱金属元素（,Na,、,K,、,Rb,、,Cs,）的区别：,(1),锂的硬度比其它碱金属都大，但与碱土金属相似。,(2),锂形成正常氧化物，而不形成过氧、超氧化合物。,(3),锂与氮气形成氮化物，其他碱金属不能与,N,2,直接化合，而碱土金属与,N,2,能直接化合。,(4),只有锂与碳反应生成,Li,2,C,2,（乙炔锂），碱土金属都能形成,MC,2,。,(5),三种锂盐（,Li,2,CO,3,、,Li,3,PO,4,和,LiF,）溶解度小，碱土金属这三种盐的溶解度也小。,二、Lithium and its compounds,二、,Lithium and its compounds,1. General properties:,6.,锂的有机金属化合物与镁的有机金属化合物相似,7.,许多锂的盐有高度的共价性，与镁相似。,8.,锂的氢氧化物、碳酸盐加热（与,Mg,相似）分解成氧化物和水或二氧化碳 ；其他碱金属的氢氧化物、碳酸盐加热难分解；而氢化锂加热不分解，氢化钠加热分解成氢气和气态,Na,2,C,2,H,5,MgBr,二、Lithium and its compoundsC2H,2. The simple substance,(1) Lithium is a soft ,silvery white metal,the,lightest of all metals,(2) preparation:,电解,LiCl(55%)KCl(45%),(3),与非金属反应,.,加热时，它直接与,S,C,H,2,反应,(4),在空气中被氧化，生成,Li,2,O,和,Li,3,N,；在,CO,2,中,加强热，可以燃烧,(5),与金属反应，生成金属互化物,2. The simple substance,氢、碱金属和碱土金属课件,(6),与,H,2,O,H,+,剧烈反应，但在水中反应会减慢，由,于,LiOH,溶解度小,(7),它是,Tritium,的来源,3.,化合物,(1) Li,的二元化合物的化学性质、溶解度和水,解性与相应的,Ca,、,Mg,化合物相似,(2) LiF,Li,2,CO,3,Li,3,PO,4,溶解度小,(3)LiOH = Li,2,O + H,2,O,这与其它碱不同，,LiOH,作为,蓄电池的电解质,Heat,(6) 与H2O,H+剧烈反应，但在水中反应会减慢，由He,(4),锂盐与相类似的其他碱金属盐形成,a.,低共熔混合物,LiNO,3,KNO,3,LiNO,3,NaNO,3,KNO,3,b.,复盐,M,+,LiSO,4,Na,3,Li(SO,4,),2,6H,2,O,(5),过氧化物（,peroxide,）不是,Li,的特征,(6)Li,的某些矿物和人造化合物可用来制备珐琅，,特殊玻璃（透过紫外光）,(4) 锂盐与相类似的其他碱金属盐形成,Graphite Intercalation Compounds (GICs),Graphite Intercalation Compoun,Graphite Intercalation Compounds (GICs),Graphite Intercalation Compoun,Graphite Intercalation Compounds (GICs),From the following article,Superconductivity in the intercalated graphite compounds C,6,Yb and C,6,Ca,Thomas E. Weller, Mark Ellerby, Siddharth S. Saxena, Robert P. Smith and Neal T. Skipper,Nature Physics 1, 39 - 41 (2005),doi:10.1038/nphys0010,Graphite Intercalation Compoun,Graphite Intercalation Compounds (GICs),Graphite intercalation compounds,are intercalation compounds with a graphite host. In this type of compound the graphite layers remain largely intact and the guest molecules or atoms are located in between. When the host and the guest interact by charge transfer the in-plane electrical conductivity generally increases. When the guest forms covalent bonds with the graphite layers as in fluorides or oxides the conductivity decreases as the conjugated sp system collapses. In a graphite intercalation compound not every layer is necessarily occupied by guests. In so-called,stage 1 compounds,graphite layers and intercalated layers alternate and in stage 2 compounds two graphite layers with no guest material in between alternate with an intercalated layer. The actual composition may vary and therefore these compounds are an example of non-stoichiometric compounds. It is customary to specify the composition together with the stage.,Potassium graphite,is denoted as KC,8,and is one of the strongest reducing agents known. It is prepared under inert atmosphere by melting potassium over graphite powder. The potassium is absorbed into the graphite and a color change from black to bronze is observed. The resulting solid is also quite pyrophoric. Structurally, composition can be explained by assuming that the potassium to potassium distance is twice the distance between hexagons in the carbon framework. The bond between graphite and potassium atoms is ionic and the compound is electrically conductive.,Graphite Intercalation Compoun,氢、碱金属和碱土金属课件,氢、碱金属和碱土金属课件,By this time, a team of researchers led by John Goodenough, now at the University of Texas, had discovered a new family of intercalation compounds based on oxides of manganese, cobalt and nickel. The first commercial lithium-ion battery, launched by Sony in 1991, was a rocking-chair design that used lithium-cobalt-oxide for the positive electrode, and graphite (carbon) for the negative one. This type of battery is now in widespread use, and,Dr Goodenough,was awarded the $450,000 Japan Prize in 2001 in recognition of his work.,By this time, a team of resear,The development of the lithium-ion battery is an object lesson in how pure and applied research, driven by commercial interests, can generate the incremental improvements in a technology that are necessary for transforming it into a useful product. In this case, intercalation compounds were an offshoot of pure research into superconductivity. They were then picked up by Dr Goodenough and other researchers working on battery technology; and the final pieces of the puzzle were supplied by Sony. (,Dr Goodenough, who did his original research at Oxford, says battery firms in the West rejected his approaches.,),The development of the lithium,三、,Sodium and its compounds,1. Existence:,2. The simple substance,(1),与,O,2,反应（过氧化物）,:,一般,2Na + O,2,= Na,2,O,2,要得到,Na,2,O,需要,Na,2,O,2,+ 2Na = 2Na,2,O,(2),熔融的钠与,S,反应,2Na + XS = Na,2,S,x,(3),钠与,NaOH(,l,),反应,2Na + NaOH = Na,2,O + NaH,(4),氨合电子,三、Sodium and its compound