I have a horror of beginning with chapter 1 on the first day of class...in any class. The reason is that chapter 1 almost inevitably does a lousy job of getting people excited and setting the tone, as you say. 

In genchem, the last couple of times, I've convened the class with the detonation of a 2:1 H2:O2 balloon, and continued by handing out blocks of dry ice, styrofoam cups of LN2, and cups of water, along with some paper towels and spatulae. I ask them to form groups of three, and...play.  After a bit of playing, I ask them to start observing...after a bit of that, I ask them to start trying to figure out everything they can about the substances. What is the "smoke" coming off the cold things? Can you tell from the way it falls in air? What is the white solid building up on the cold stuff? Which is coldest, and how do you know? As they're doing this, I talk about Baconian science, and how what separates chemistry from alchemy is that in chemistry, we build up our grand ideas from small observations. That what they are doing-playing with stuff like 8-year-olds...is the root of modern science. Observing the world and trying to figure out what it means is the core of science. We invent theories to explain what we see, hear, and smell. I try to encourage them to think about chemistry as a process of observing, educated guessing, and testing, instead of facts to be learned.

In Inorganic, I talk about how I like the class to function (essentially as one big group working on questions, problems, and papers together...I lecture far more minimally in that class), and, again, try to instill a sense of wonder. The last time I taught it, I filled a big dish with mercury (don't tell OSHA), floated nails on it, then floated lead shot on it (don't try this at home-it contaminated the mercury with lead and the lead with mercury...I now have a container of lead-laced mercury I use for this). I usually follow this up with a discussion of the idea of a "model" and why we might use "wrong" models a lot of the time. In the next week, we then launch into Lewis theory, Valence Bond, and MO.

In Gen Chem, I usually try to spend just a little time, building the wonder and excitement and setting the frame of reference for the class – our goal will be to gain a molecular view of the world and to try to build our understanding of observations on the molecular level.  A few key demonstrations always work nicely.  I'm not an explosions chemist, so while my colleague reaches for the H₂/O₂ balloons, I look for more "passive puzzles."

Examples I have used in the past include:

• Why does your pencil write?
• Take a large beaker of water and show them a can of Coke and Diet Coke before immersing each in the beaker.  Why does that happen?
• Hmm DCM (Diet Coke and Mentos) might be very handy here...
• Coin-operated Red, White, and Blue demo from Shakashiri, vol 3, Demo 8.9: loads of chemistry here to cover in Gen Chem
  
• Lately, we start off with "What's in a Star" so I show some beautiful images from astronomy
  

In gen-chem this year, I started with the Mg/dry ice demo (http://www.ilpi.com/genchem/demo/co2mg/index.html). (tip: be CAREFUL of the amounts you use in the room you're going to do it in--i.e. ventilation, fire alarm system, and size of demo table!)   I used it as a springboard to talk (review) states of matter, physical vs chemical transformation, periodic table trends, balancing an equation and endothermic/exothermic.  During the course of the demo, I prompt students through the scientific method (most catch on why we're "guessing" what will happen), so I also review that.  They mostly all remember from high school all of these terms/concepts, but seeing it in action is cool!  Plus, as one student said this year, "You know any kind of class that fills the room with smoke on the first day is going to be good."