94年國立台灣師範大學化學所有機化學

How many stereoisomers of tartaric acid, HOOCCH(OH)CH(OH)COOH, arepossible?

2

3

4

6

8

Ⅰ Ⅱ Ⅲ Ⅳ

Ⅱ Ⅰ Ⅲ Ⅳ

Ⅳ Ⅱ Ⅰ Ⅲ

Ⅳ Ⅰ Ⅱ Ⅲ

Ⅰ

II

III

IV

The process of separating a racemic mixture into the pure enantiomers (opticalresolution) requires the used of a resolving agent. Which of the followingcompounds CANNOT be used as a resolving agent.

(1R)-(−)-10-Camphorsulfonic acid

(1R)-(+)-10-Camphorsulfonic acid

(R, R)-(+)-Tartaric acid

(R)-1, 1-2-Trimethylcyclohexane

(R)-Lactic acid

Which of the following compounds in NOT aromatic?

2S, 3R

2S, 3S

2R, 3S

2R, 3R

Which of the following statement is NOT correct?

Enantiomers are stereoisomers whose mirror images are mot identical, thatis they are not supoposable

Only carbon atom can be a chiral center

Polar aprotic solvents are capable of forming H-bonds that can dissolve anionic solute

The extraordinary stability of the allyl-type radical is due to the resonanceeffect

Alcohol dehydratins usually go through E1 elimination and the reactivity is:3° > 2° > 1°

Which of the following molecule has NO dipole moment?

SO₂

NH₃

CO₂

CH₃COCH₃

CH₃COOCH₃

Which of the following IUPAC name is NOT correct?

Which of the following statements is NOT correct?

Carboxylic acid tends to form dimers by intermolecular H-bonds

Ketones are more reactive toward a nucleophile than that of amides

β-Dicarboxylic acid is prone to decarboxylation through a cyclic transitionstate

Robinson annulation involves three steps: Michael addition, aldol reactionand dehydration

Lewis base can be used to catalyze Friedel-Crafts alkylation of aromaticrings

Using Newman projections to draw the most stable and least stableconformation of 2, 5-dimethylhexane? (looking along the central C3-C4 bond).

Draw the most stable conformation of the following molecules.

Explain why trans-2-bromocyclohexanol reacts much faster to formepoxycyclohexane compare to that of cis-2-bromocyclohexane.

The experimental observation found that maleic anhydride and cyclopentadienegive the endo adduct faster than they give the exo adduct, even though the latteris thermodynamically the more stable. Please draw and label the endo and exoisomers ofthe Diels-Alder adduct of cyclopentadiene and maleic and explainthis observation.

The Hammett free-energy relationship is expressed as the following equations.The σ value can measure the ionization of the substituted benzoic acid and thatof benzoic acid itself and the ρ value reflects the sensitivity of the particularreaction to substituent effects.

Hammett eaquation: log K/Ko = ρσ or log k/ko = ρσ
σx = log K − log Ko
= pKa (C₆H₅COOH)−pKa (X−C₆H₄COOH)
= −pKa + (pKa)o
Based on above description, please list all the procedures and calculate thefollowing questions.

(1) The pKa of p-chlorobenzoic acid is 3.98; that of benzoic acid is 4.19.Calculate σ for p=Cl. 
(2) The ρ vale for alkaline saponification of methyl esters of substitutedbenzoic acids is 2.38, and the rate constant for saponification of methylbenzoate under the conditions of interest is 2 X 10⁻⁴ M⁻¹s⁻¹. Calculate therate constant for hydrolysis of methyl m-nitrobenzoate. (σm−NO2 =0.71)

An organic compound has the molecular formula C₁₀H₁₄. Identify the thecompound using the spectroscopic data given below.
νmax (liquid film): no significant features in the infrared spectrum.
λ max: 265 (log ε: 2.3) nm. ¹H NMR (CDCl₃ solution): δ (ppm) 7.1, m, 5H; 2.5,apparent sextet, J = 7 Hz, 1H; 1.6, apparent quintet, J = 7 Hz, 2H; 1.22, d, J = 7Hz, 3H; 0.81, t, J = 7 Hz, 3H. ¹³NMR (CDCl₃ solution): δ (ppm) 148.4 (C),129.3, 127.9, 126.1, 42.3 (CH), 31.7 (CH₂), 22.2, 12.2 (CH₃), Mass spectrum:m/e 134 (M⁺, 20), 119(8), 105(100), 77(10).

對於一連串的實驗數據以最小平方法(the least-squares method)導出校正曲線時，除可以使用市售的Excell 軟體以外，也可以用電子計算機計算。用電子計算機計算的過程中，下列哪一個公式是不需要的呢？

當有一個數據含有偏遠結果，而且出現在離平均值很遠的地方。如果我們必須決定這數據到底是要保留或拾棄時，可以使用統計學上的一些Test 來加以判斷。試問，下列各種統計學上的公式，哪一個公式符合這樣的需求？

磷酸鹽、碳酸鹽……等鹽類在水中的溶解度受到pH 的影響甚大……。試問在pH = 4 的緩衝溶液中，草酸鈣(CaC2O4)的莫耳溶解度(s)為何？已知下列一些有用的關係式：

3.0 × 10⁻⁵M

4.0 × 10⁻⁵M

5.0 × 10⁻⁵M

6.0 × 10⁻⁵M

7.0 × 10⁻⁵M

在下列的計算例題：『Use activities to calculate the hydroninm ionconcentration in a 0.120 M solution of HNO₂ that is also 0.05 M NaCl. What isthe relative percent error incurred by neglecting activity corrections?』計算過程中，下列哪一個公式是不需要的呢？

3.0 × 10⁻⁵M

4.0 × 10⁻⁵M

5.0 × 10⁻⁵M

6.0 × 10⁻⁵M

7.0 × 10⁻⁵M

由順丁烯二酸(H₂M) pH 值與α值的函數圖形中，試由看圖寫出順丁烯二酸的pKa₁ 與pKa₂ 的值，大約多少？

利用單點標準添加法(single-point standard addition method)及鉬酸藍法(molybdenum blue method)可以分析磷酸根離子。今有2.0-ml 的尿液樣品以鉬酸藍法處理過後，形成藍色的鉬酸藍錯合物，吸收波長為820nm。隨後將此樣品稀釋到成為100mL 的溶液。取其中的25.0-mL(溶液1)進行吸收光譜的測定，得到吸收度為0.428。再取另外的25.0-mL(溶液2)，並加入含0.05mg 的磷酸根離子的1.0-mL 溶液，再測量一次吸收度，得到0.517。試問，尿液樣品中磷酸根離子的濃度為何？

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9 mg/mL

計算0.01M 的NaH₂PO₄ 溶液中的[ H₃O⁺ ]，可以用下列哪一個公式計算？

電位滴定分析可以用數種方法來決定滴定終點，最直接的方法就是將電位與滴定試劑的體積畫成函數圖形。例如，下列的函數圖形就是記錄以硝酸銀滴定氯離子的情形。試分別簡單畫出此圖形經過『一次微分』及『二次微分』後的圖形。做此微分操作有何用處？

在分析儀器中常用運算操作器做訊號的放大(multiplier)、相減去除雜訊、相加、或訊號微分器、訊號反相器及訊號對數化放大器等工作。下列哪一種IC 為運算操成器中經常使用到的元件呢？

ADC0801

556

AD8255

LM334

LM335

S740

5566

OPA1458

下列哪一個線路圖是放大訊號用的電子線路圖呢？

沉澱滴定法中最常被用的方法之一就是銀滴定法。這方法是以硝酸銀為沉澱劑，主要應用於鹵離子、類鹵素陰離子(如SCN⁻，CN⁻，CNO⁻)、硫醇、脂肪酸等的分析。常用的化學性“指示劑”包括：

 鉻酸根離子：Mohr 氏法(生成有色沉澱)
 吸附指示劑：Fajans 氏法(吸附指示劑法)
 三價鐵離子：Volhard 氏法(生成有色錯合物)

加入的指示劑：(A)螢光黃 (B) CrO42⁻ (C) SC^l− (D) Fe³+ (E)環糊精
(1) 答案( )單選題

(2) 答案( )複選題

(3) 答案( )複選題

滴定終點時的顏色變化：(F)白色變黃色 (G)黃色變白色(H)白色變紅色(I)紅色變白色(J)紅色變黃色(K)黃色變紅色

(4) 答案( )單選題
(5) 答案( )單選題

飛行時間型質譜儀是一種常見的高靈敏度質譜儀。如果利用基質輔助雷射脫附離化或電灑離化的方式，可以將巨大分子量的樣品，例如蛋白質、DNA、聚合物……等，順利的導引進入質譜儀中進行測量。試簡單畫出並說明(限中文40 字以內)：

(1) 電灑離化式−飛行時間型質譜儀
(2) 基質輔助雷射脫附離化−飛行時間型質儀

說明下列各種分析儀器之偵測原理並繪出其儀器結構示意圖：
(1) ESCA (Electron Spectrometry for Chemical Analysis，化學分析電子光譜儀)檢測丙醛各碳原子狀態。
(2) SEM (Scanning Electron Microscope，掃瞄式電子顯微鏡)檢測Au 奈米粒子。
(3) AFM (Atomic Force Microscope，原子力顯微鏡)檢測矽晶片表面。
(4) ICP (Inductively Coupled Plasma) Emission Spectrometry (誘發耦合電漿發散光譜) 儀偵測水樣品微量Cu(Ⅱ)離子。

紅外線(IR)及核磁共振儀(NMR)為化學研究常用儀器。

(1) 說明FTIR (Fourier Transform-IR，福傳式紅外線光譜)儀之偵測原理並繪出儀器結構示意圖。
(2) 比較下列兩組中之兩原子間振動(Vibration)之紅外線吸收基本振動頻率(Fundamen Vibrational frequency，此頻率可用波數cm−1 表示)之大小順序：

 C – H, C – D, C – Br, C – Cl, C – F,
 C − N, C = N, C ≡ N

(3) 比較IR 及Raman(拉曼)光譜分析儀之偵測原理不同，及儀器元件(如光源，樣品槽材料及偵測器等)之不同。
(4) 說明FT-NMR (Fourier Transform-NMR，福傳式核磁共振儀)儀器偵測原理並繪出儀器結構示意圖。
(5) 說明醫學診斷常的MRI (Magnetic Resonance Image，磁共振顯像)儀用來側測腫瘤之檢測原理及所偵測的項目。

下列各種層析法所用元件及層析儀之偵測原理並繪出其儀器結構示意圖：
(1) 膠透層析GPC (Gel Permeation Chromatography)儀偵測高分子之分子量。
(2) 超臨界流體層析SFC (Super-Critical Fluid Chromatography)儀分離各種有機物。
(3) FID (Flame Ionization Detector)偵測器偵測有機物RH。
(4) ECD (Electron Capture Detector)偵測器偵測有機氯化物RCl。