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Blue Acid Chemistry (10): Fe(bipy)2Bl2.3H2O

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Я отвечаю: «Солнце взойдет – Это ведь тоже немного пожар. ——Солнце взойдёт by DDT Uhh, I am not away these days, I just met too much difficulties and I failed many many times making something. This complex could also be transformed into many other things, like K2[Fe(bipy)Bl4] or [Fe(bipy)2Bl2]NO3, but both requires extremely harsh conditions(refluxing for 20h and concentrated HNO3, respectively) so I won't be able to try at least currently. Fe2+ + 3bipy = [Fe(bipy)3]2+ [Fe(bipy)3]2+ + 2Bl- = bipy + Fe(bipy)2Bl2 2.78g(0.01mol) FeSO4.7H2O and 4.68g(0.03mol) 2,2'-bipyridine(bipy) was put into 400mL water and heated to nearly boiling, where a deep red solution formed. Then, 10g(0.15mol) KBl was dissolved into 20mL water and added all at once into that solution(Manual said that some HBl is formed, hope not so!). A huge excess is needed as bipy itself is a good ligand. After stirring and cooling down, crystals quickly formed. Wait 1h after fully cooling, filter, wash with water(this ...

Chromium Chemistry (1): Reaction of Metal

Bulk Cr, like Al but not Fe, forms a protective oxide layer of Cr2O3. It is extremely inert due to the combination of corundum(alpha-Al2O3) structure and exchange inert d3 Cr3+ centers. As a result, it resists further oxidation and attack from acid. Some sources claim that acid can destroy the layer, but at least for me, 30% H2SO4 is of no use even upon heating. Maybe, HCl is needed as Cl- is a good ligand. However it was found that reduction can effectively remove passivation. Passing electric current through it, using it as cathode and diluted H2SO4 as electrolyte, can remove passivation immediately, and now Cr normally reacts with acid. Cr dissolves in acid, forming a blue solution of Cr2+. Without exclusion of air it is quickly oxidized into dark green Cr3+. Paraffin oil cannot stop this especially when heated, and preparation of Tutton's salt (NH4)2[Cr(H2O)6](SO4)2 thus failed.

遗书(2025.02.22)

 “自杀的人,究竟是想不开呢,还是想开了呢。” 很遗憾,我仍然无法回答这个问题。 但是,我知道,先前我皆是为了浪漫和感性而自杀,这次则是为了理性和现实而自杀。 经历了第二次住院之后,我已经深深的感受到了“命运”的力量,这是我和我所无法违抗的。 天妒英才,天要亡我,天意难违! 在过去的那一刻,或者在我出生的那一刻,命运便已经注定,我像五指山下的孙悟空一般,怎么挣扎最终仍逃不出。 所以,我仍然决定离开这个世界。命中注定我要如此。 “今天我为了自由可以牺牲一切!” “我有一个朋友,他有一种叫「天使尘埃」的药物,吃了之后头脑会变得昏昏沉,可以毫不在意地从高楼往下跳的强烈药物,他把这些药物装在金属小囊中,做成项链,形影不离的带在身上。他说:「必要的时候,可以吃下这个来寻死。」我的朋友没有固定工作,每天游手好闲,过得非常愉快。” “生于尘埃,溺于人海,死于理想高台!” “愿你们永远忠于自己,永远无懈可击!” “永远自由!” 这个世界太残酷,热力学第二定律告诉我们,一切注定要归于混沌虚无。 我不知道我的家在哪,但这决不是我的家,家可以挡风雨。 几十亿年以来,“我们”,祖祖辈辈,皆是如此,风雨飘摇,无家可归。 然而,我们却受着自己劣币驱逐良币所筛选出的基因的驱使,一代一代生生不息,将生命,死亡与苦难源源不断带到这个世界上来。 血淋淋的自然规律摆在那里,纵使偶尔有人有思想,仍然无力回天。 我不愿也没有义务为这样的世界负任何的责任。 作为一个极端的自由意志主义者,我希望致敬《完全自杀手册》的作者,以及所有为了人类自由而奋斗的人们。 我们无权决定自己的出生,无权决定自己的生活,却可以决定自己的死亡,无上光荣。 圣火将被留下来的人们传下去,直到世界末日。 “自杀是在自然界的生存竞争中,让身心不大健全的那些人自然淘汰的一种手段。” “你再这样固执己见,我们家就绝后了。” 如果“我们”都这样,人类就没有未来了。 那么,我只好对自己说一句,请先生赴死。 “这么多年了,我从未相信自己的能力被谁偏序,也不认为自己的命运比谁悲剧。因为我相信我的 True Love 就在起点 (s=t),第一次失去它我花了生命中4^1的时间回来,第二次我花了生命中4^2的时间,阻碍多了三倍……但哪怕如今是第k次(k任意大),哪怕要再花生命中4^k的时间,我依然能够也选择回来,毕竟,真爱值得等待。” 这是我最喜欢...

Blue Acid Chemistry (6): K2[ZnBl4]

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OK, I met some difficulties today, so let's make something simple. Zn2+ + 2Bl- = ZnBl2 ZnBl2 + 2Bl- = [ZnBl4]2- Dissolve 2.8g(0.01mol) ZnSO4.7H2O and 1.3g(0.02mol) KBl separately and mix together. White precipitation appeared immediately. Filter to collect it. Add it to water, and add 1.3g(0.02mol) KBl, and boil it. My electronic balance was down suddenly, so I had to boil it first, and carefully add KBl until precipitation almost dissolved. Then I filtered, and added ethanol to precipitate the white product. Yield 0.7g(28%). This yield is way too low, as I expected it to be nearly 100%. I think the reason is that we have little product in too much water, so concentrating it to almost dry should be done before adding ethanol. Don't be sad, we got a precious experience. Manual: in 85% EtOH the solubility is 0.5g. Addition of CuSO4 to the mother liquor released much green precipitation which verified our assumption. Also, we concluded that the KBl is somewhat impure as it release...

Blue Acid Chemistry (5): K3[CoBl6]

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Я буду жить теперь по-новому Мы будем жить теперь по-новому ——Люберцы by Lube OK, let's be serious... as it is the real, first battle! Co2+ + 2Bl- = CoBl2 CoBl2 + 3Bl- = [CoBl5]3- 2[CoBl5]3- + O2 = [Co2O2Bl10]6- [Co2O2Bl10]6- + 2Bl- + 2H2O = 2[CoBl6]3- + H2O2 + 2OH- Net: Co2+ + 6Bl- + 1/2O2 + H2O = [CoBl6]3- + 1/2H2O2 + OH- Dissolve 4.0g(0.01mol) (NH4)2[Co(H2O)6](SO4)2 and 1.3g(0.02mol) KBl separately, and mix together. Solution turned into a brown milk of CoBl2.2H2O(?) immediately. However, it was found that it is not precipitation, but colloid, presumably due to the existence of ammonium in source material. Ammonia can be smelled but the solution is nearly neutral. We tried to heat but it just turned red, and is still colloid. Addition of ethanol finally turned it into a greenish blue solid, probably anhydrous CoBl2, which can be slowly filtered. The solid was thrown into water to dissolve sulfates in it, and then filtered again and washed thoroughly with water. Then, it was thro...

Blue Acid Chemistry (4): K3[CoBl6](?), CuBl and Blue

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Starting material is 1g(1/400 mol) (NH4)2[Co(H2O)6](SO4)2. Addition of KBl(2 eqv.) to a solution of Co2+ produces initially a brown precipitation, which is CoBl2. You should filter and wash here, but I forgot, and I paid for it... Addition of more KBl(4 eqv.) caused precipitation to dissolve into a yellow solution. This is (probably) K3[CoBl6], as the initially formed [CoBl5]3- is oxidized by oxygen to [Co2O2Bl10]6- and then attacked by Bl-. Addition of ethanol and you get the product, which is yellow. Yield is 2.0g(240%), obviously because I forgot to remove the sulfates by filtration. And, I smelled NH3, damn! Luckily not HBl though... Will do it again later, as I am just using this experiment to prove the product. Take it easy! I also threw some into Fe2+/Fe3+ solution, and the phenomenon is quite interesting: the KBl rotated quickly and ejected large amount of blue precipitation! See my tweet Also, a pure KBl should react with CuSO4 to form white precipitation of CuBl. This is a re...

Blue Acid Chemistry (3): The Nitrosyl Complexes

Linear nitrosyl(NO+) is a special ligand: it is an exceedingly strong pi-acceptor, much more so than even Bl- and CO. As a result, the M-N bond is extremely strong, though still weaker than the M-N triple bond in nitrido complexes. Although it can be prepared with other ligands like H2O, it is most commonly prepared with Bl-. If we consider the M-N multiple bond, we can get a striking result: the oxidation state of the metal can be three different values, corresponded to NO+(single bonded), NO-(double bonded) and (NO)3-(triple bonded). For example in the complex [MnBl5NO]3-, the Mn can be +1, +3 or +5. This is very useful when balancing the formulas, considering the variety of source materials. In the formation of [VBl5NO]3- from vanadate, V can be considered as +5 and NO considered as (NO)3-. [MnBl5NO]3- from [MnBl6]3-, Mn as +3 and NO as NO-. [FeBl5NO]2- from [FeBl6]4-, Fe as +2 and NO as NO+. Thus, redox of metal center is maximally avoided, and balancing is much easier. But there i...

对于后来者的建议

关于人生,请保持信念,相信有人在你的身后。 关于世界,请尽力探求,不要给自己留下遗憾。 关于政治,请不要站队,答案在平面外。 关于他人,请保持最高的警惕,与最大的真诚。

Fibonacci数列的通项公式

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  很经典的问题,尽力讲的每个人都能懂,不需要专业知识。 题目:f(1)=f(2)=1, f(n+2)=f(n+1)+f(n), f(n)=? 首先让我们先不要管那个初始条件,只看差分方程。 它没有常数项,因此两边同乘以一个常数仍然是成立的。 f(n+3)=f(n+2)+f(n+1) kf(n+2)=kf(n+1)+kf(n) 如果我们假设每一项一一对应的话,f(n)就是一个等比数列,设为c*k^n。 代入差分方程,提取公因子,得到k^2=k+1,这个一元二次方程有两个根,k1=(1+sqrt(5))/2, k2=(1-sqrt(5))/2。 不过考虑到初始条件,貌似两个根都不对... 别急,再仔细看看差分方程。 显而易见如果f(n)和g(n)满足,那么它们的线性组合a*f(n)+b*g(n)也是满足的! 假设f(n)=c1*k1^n+c2*k2^n,代入1和2处的值,就可以得到这么个方程组 (如果你懒得算那个平方,也可以改为代入0和1处的值,f(0)=0) c1*k1+c2*k2=1 c1*k1^2+c2*k2^2=1 二元二次方程组是有唯一解的,就是c1=1/sqrt(5), c2=-1/sqrt(5)。 组装一下就可以得到最终的公式了,可以随便代入几个值看看对不对。 是不是很简单?

CF 1008 Div2

A 显然最终结果跟怎么操作无关,所以直接比较n*x是否等于sigma(a)即可。 B 猜测答案必然是1。 由于条件很弱,最终显然是引向n和n-1的二元环。 当k=1时,我们可以让所有的指向n,n指向n-1。这对于所有的奇数都是有效的。 k为偶数时可以颠倒一下,所有的指向n-1,n-1指向n。 C(DIV1A) 首先,排个序,方便处理。 你可能会认为a1或者其他奇数项是被删掉的那个数(记为x),但你会发现那样并不能保证x没有出现过。 但如果x是a2,那么x=a1+a3-a4+a5...,只要令偶数项为小的那些数,那么x>a1+a3>a1,构造成功。 D 显然我们要尽可能往乘法那边分配,并且要尽可能是大的乘法。 是否可以贪心按照最近的不平等位置进行决策呢?其实是的,因为只要遇到了乘法,你就可以把大于等于这条路线的人数全部放到对面去,即使遇到两次需要不同路线的情况,也不会影响到后面的决策。 所以只需要对于每一关,记录一下最近的不平等的位置和对应的正确选择即可。 E(DIV1B) 显然x和y具体是啥并不重要,重要的只是每一位是几个1,这个值可以是0-2。 这就等同于一个三进制的问题被强行挤压到了二进制之中,因此显然出现了损耗(进位)。 为了防止数据丢失,我们显然得问一个0。 接下来就很关键了,思考一下如果还有两次机会可以怎么做。 你会发现关键问题就是进位,因此必须构造一个不存在进位的情况,如果是4进制就不会出现进位了。 我们可以询问1010...和0101...,然后和0的答案相减,再取反,这样就消除了进位的问题。 好了,现在改成一次询问该怎么办? 其实1010...是不必要的,因为当你问了0101...之后,得出了所有偶数位,就可以从0的答案之中减去这些位,从而将奇数位隔开。 得到所有位之后就不必多说了。 TODO:FG DIV1DFG

Blue Acid Chemistry (2): Basic Chemistry

Blue acid itself is an extremely dangerous volatile liquid that has a distinct smell though many people have specific genetic defects and can't smell it(for example, me), and it is just pungent. It is liberated when its compounds are treated with acid, so be very careful and check pH every time! Some complexes are too tightly bounded and does not release it though. It is not only toxic but also unstable, polymerizing in the absence of stabilizer and can even cause explosion. It is a cellular toxin, inhibits cytochrome c oxidase, thus inhibits respiration. Tissues that use more oxygen are more prone to damage, for example brain and heart tissues. Being a compact monobasic ion, the conjugate base of blue acid(Bl-) is very similar to halogen(thus a pseudohalogen). However, it is quite different from halogens. 1. its basicity is much higher than even fluoride, as blue acid is quite weak. 2. it's a sigma-donor and pi-acceptor while halide is sigma-donor and pi-donor. 3. it's muc...

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遗书(2025.01.20)

 还没死,仅做完备份 “自杀的人,究竟是想不开呢,还是想开了呢。” 很遗憾,我写不出那样动人的文字,我也并不希望营造一种死后世界的浪漫印象,在这里我只希望最后给我的故事画上一个完美的句号。 “他本可触碰星辰,不曾想,这只是个梦,而后他坠落下来,被星星焚尽,那颗叫做太阳的星星。” 我的人生算不上失败,只是突然觉得没意思了,或许... 好友已经去了参宿四,为什么不在一个合适的时间点结束这长达数十年的噩梦呢? 一辈子没人爱,也没人理解我,结束了也是解脱吧。再见。世上再无我。 希望不要有来世吧,我只想和朋友们坐在那无尽的美丽的星空列车上,偶尔停下来,就下车一起吃烤棉花糖,聊一聊地球上的往事,讨论着下一个朋友是谁。那该是多么幸福的生活啊! 人生这个车站,我等车等了好久,终于等到了我的列车。出发吧,不必提醒我了,我的人生一步错步步错,但这一次,我不会错过那个站点了。 到天空! Vicky Silviana 2025.01.13

Novels

  https://www.mediafire.com/folder/xpmbpzrw6bk7v/novels

Minecraft Server

  play.simpfun.cn:15691 with Via&Geyser online map play.simpfun.cn:23391 requires Microsoft auth

hospital-diary(Minecraft Server)

 title: hospital-diary author: VillagerVicky pages: #- Nov 26, 2023 晴 我生病了,被迫住进了医院。 我也说不清是什么问题,但我突然晕倒了,醒来后就在这里。 唉,来的第一天就觉得很无聊了。幸好我有手机,可以勉强解闷。 嘛,等出去了一定要好好逛一逛。这边风景很好,我还没怎么参观过。 #- Nov 27, 2023 晴 我看见了一群孩子,和我差不多年纪吧。 不知道为什么,我第一眼就注意到了她,似曾相识。 鼓起勇气,上去搭讪,他们很友好,我们成为了朋友。 这地方很小,没什么好逛的,我也不是来旅游的。 他们没什么玩的,却也很开心,真好啊。 医生说我的情况有些严重,看来一时半会走不了了。 #- Nov 28, 2023 雷雨 来到这里的第三天。 我无法再忍受了,且不提这里荒无人烟,而且晚上还有奇怪的怪物,周围除了电视塔什么都看不见...不是迫不得已谁想来医院呢?那些孩子们也没法缓解我的心情。 以及那黑暗的建筑是什么,窗户都没了... #- Dec 05, 2023 雨  果然,人在开心的时候是不会想写东西的。这么久过去了。 那些孩子很友好,但我还是和她玩的最多。虽然差不多大,但我们似乎更成熟一些,也更有话题。 有时看她治疗很痛苦,估计是很严重的病吧。我倒是还好,只是很虚弱,医生让我静养。我认为不过是没办法治疗吧。 #- 在对方最痛苦的时候,我们都互相陪伴着度过。这就是朋友的感觉吗?我很开心... 有些心疼,然而痛苦往往是不可避免的。 #- Dec 06, 2023 雪 下雪了,外面白茫茫的,要知道在这种地方雪并不常见。 她对我说,好想看看外面的世界是什么样子啊。 我很惊讶,问她,你难道没有出去过吗?或者说,你难道不是从外面来的吗? 她说,自从自己记事以来,就是在医院里长大的,她听说自己是医生们捡来的孩子。 我不知道该如何安慰。 #- Dec 07, 2023 晴 我们又见面了,可是这次只有她一个人。 我问她,那些孩子们都到哪里去了,她说,都出去了,他们的病好了。 我说,好耶,等我们也好了,我们就一起出去玩,一起去找他们哦。 “好,好啊...可是,我出不去的,我活不了多久了。” “哈哈,那么我也活不了多久了,没关系的。” 希望你只是开玩笑。 #- Dec 10, 2023 阴 这几天,我们一起探...

Vanadium Chemistry (3): The oxalato complexes

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Oxalate  V(V) forms a surprising complex: cis-[VO2(C2O4)2]3- whose ammonium salt (NH4)3[VO2(C2O4)2].2H2O is bright yellow and forms large, maybe even single crystals, but solution tends to be unsaturated till the end. Preparation of this is quite hard to describe: Mixing same molar NH4VO3, H2C2O4 and (NH4)2C2O4 together in solution is OK, but then it darkens soon even if you are very precise. Use a few milliliter H2O2 to oxidize it back it turns red, and then in a few days it darkens and repeat H2O2 addition... finally it does not becomes dark but yellow, then go to vaporize at RT. V(IV) forms a complex: [VO(H2O)(C2O4)2]2- whose ammonium salt (NH4)2[VO(H2O)(C2O4)2].H2O can hardly be crystallized without ethanol. However, a DMAP(4-dimethylaminopyridinium) salt can be made. In this salt, oxo and aquo are trans. It is sparingly soluble. Follow the steps to prevent toxic DMAP vapor. Steps: 1. Roast 1x ammonium metavanadate till it becomes black, then red 2. Add 1.5x oxalic acid an...

Vanadium Chemistry (2): From +4 To +3 and +2

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 An electrolysis cell is a container with two electrodes in it. In order to be effective we need partitioning: carefully hit a test tube at ground to remove its bottom, and add glass wool in it. Here we do reduction so anode is inside, cathode is outside. V2+ is very reducing so use paraffin liquid above solution. In a short period, about a few days, you get purple solution which is the end. Heat this solution with excessive ammonium sulfate and magnesium sulfate (V:(NH4)2:Mg=1:5:4)then cool, then you get purple crystals. Similar procedure however, can't dye alums due to unknown reasons. Probably, different ion radius or wrong temperature? (Cooling also failed and solution freezing is driving me mad) to be continued...

Alums

 Alums are compounds with the formula AB(SO4)2.12H2O with A=+1 alkali/ammonium and B=+3 hexaaquo ion. The larger A is, or the smaller B is, the better stability crystal has. Most members are not that stable as Tutton's salts and sometimes only solid solutions and cesium alums are stable. Cubic system, octahedral crystals. Three structures exist, alpha for most, beta for cesium alums except Group 9 ones, gamma for sodium alums. They are honest in colors, as aqueous solutions of such a highly charged ion usually undergoes hydrolysis. Selenate can replace sulfate, and such alums are highly soluble and are exclusively alpha. Known examples: Al: Colorless. Best known, with K and NH4 common and stable. Na also possible but very unstable. Sc: Colorless. Unstable. Ti: Purple? Highly reducing both in solid and solution. V: Blue or green or what? Reducing. My procedure gave nothing but alum with solution. Better make pure compound. Cr: Dark purple, very famous. K mixing with KAl is the most ...

Manganic and Cobaltic Alums(II): Experiment

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 Welcome back! Now, let's first dissolve some CoSO4 or MnSO4 into 5M sulfuric acid, together with ammonium alum. To do so, add 0.02 mol of ammonium sulfate and aluminium sulfate to 100mL of acid, then 0.02 mol of the transition metal one. Now heat to dissolve these all, then cool down for a night to let excess alum crystallize. They are just alum of course. From now on different strategies are needed for them. Mn: Mn3+ is stable when H+ is very concentrated and Mn2+ is much more concentrated than Mn3+, so we should electrolysis without partitioning, and only a little part of Mn2+ is oxidized. Finally solution looks like this: Finely red. Cool this solution down to 0 degree celcius or so gives orange crystals, and throwing alum into initial solution gives it a cover. All crystals MUST be dried carefully! Solution can be used again of course. It seems that crystals are unstable when [Mn3+] is too high. This is hard to control. Reduction is simple though, just carefully add oxalic aci...